EP4363479A1 - Recovering di- and/or polyisocyanates from pu-depolymerisation processes - Google Patents
Recovering di- and/or polyisocyanates from pu-depolymerisation processesInfo
- Publication number
- EP4363479A1 EP4363479A1 EP22738453.4A EP22738453A EP4363479A1 EP 4363479 A1 EP4363479 A1 EP 4363479A1 EP 22738453 A EP22738453 A EP 22738453A EP 4363479 A1 EP4363479 A1 EP 4363479A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- carbon atoms
- radicals
- hydrogen
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 45
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 claims abstract description 111
- 229920002635 polyurethane Polymers 0.000 claims abstract description 98
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 90
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229920000768 polyamine Polymers 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 150000003871 sulfonates Chemical class 0.000 claims abstract 4
- 239000006260 foam Substances 0.000 claims description 141
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 96
- 239000012948 isocyanate Substances 0.000 claims description 70
- 150000002513 isocyanates Chemical class 0.000 claims description 68
- -1 polymethylene Polymers 0.000 claims description 66
- 229920005862 polyol Polymers 0.000 claims description 63
- 150000003077 polyols Chemical class 0.000 claims description 60
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 58
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 150000003254 radicals Chemical class 0.000 claims description 32
- 150000005840 aryl radicals Chemical class 0.000 claims description 26
- 239000011496 polyurethane foam Substances 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 25
- 229920006395 saturated elastomer Polymers 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 239000004604 Blowing Agent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001033 ether group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- KPPVNWGJXFMGAM-UUILKARUSA-N (e)-2-methyl-1-(6-methyl-3,4-dihydro-2h-quinolin-1-yl)but-2-en-1-one Chemical compound CC1=CC=C2N(C(=O)C(/C)=C/C)CCCC2=C1 KPPVNWGJXFMGAM-UUILKARUSA-N 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- COPLXRFZXQINJM-UHFFFAOYSA-N isocyanic acid;hydrate Chemical compound O.N=C=O COPLXRFZXQINJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005829 trimerization reaction Methods 0.000 claims description 3
- FCQPNTOQFPJCMF-UHFFFAOYSA-N 1,3-bis[3-(dimethylamino)propyl]urea Chemical compound CN(C)CCCNC(=O)NCCCN(C)C FCQPNTOQFPJCMF-UHFFFAOYSA-N 0.000 claims description 2
- MPJZCYUPWINKPK-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octan-3-ylmethanol Chemical compound C1CN2C(CO)CN1CC2 MPJZCYUPWINKPK-UHFFFAOYSA-N 0.000 claims description 2
- NCUPDIHWMQEDPR-UHFFFAOYSA-N 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol Chemical compound CN(C)CCOCCN(C)CCO NCUPDIHWMQEDPR-UHFFFAOYSA-N 0.000 claims description 2
- IIVBUJGYWCCLNG-UHFFFAOYSA-N 3-(dimethylamino)propylurea Chemical compound CN(C)CCCNC(N)=O IIVBUJGYWCCLNG-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000306 component Substances 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000011493 spray foam Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- XOUUBIIWXXBSJN-UHFFFAOYSA-N 1-[3-[bis[3-(dimethylamino)propyl]amino]propyl-(2-hydroxypropyl)amino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)CCCN(CCCN(C)C)CCCN(C)C XOUUBIIWXXBSJN-UHFFFAOYSA-N 0.000 claims 1
- DNRUQHYIUPKPOQ-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethoxy]ethyl]-n'-methylpropane-1,3-diamine Chemical compound CN(C)CCOCCN(C)CCCN DNRUQHYIUPKPOQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 description 27
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 14
- 238000009472 formulation Methods 0.000 description 11
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 238000005187 foaming Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000004971 Cross linker Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 6
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 3
- 239000013518 molded foam Substances 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 2
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
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- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- MHRLWUPLSHYLOK-UHFFFAOYSA-N thiomorpholine-3,5-dicarboxylic acid Chemical compound OC(=O)C1CSCC(C(O)=O)N1 MHRLWUPLSHYLOK-UHFFFAOYSA-N 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- QRQSVPNWQIQYJB-UHFFFAOYSA-N triisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)(N=C=O)C1CCCCC1 QRQSVPNWQIQYJB-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GRTDTECCKHJLNJ-UHFFFAOYSA-N undecane-1,1,6-triamine Chemical compound CCCCCC(N)CCCCC(N)N GRTDTECCKHJLNJ-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention is in the field of di- and/or polyisocyanates, polyurethanes and polyurethane recycling.
- a process for preparing aromatic and/or aliphatic di- and/or polyisocyanates is described, which starts from the depolymerization of a polyurethane by hydrolysis.
- polyurethanes Due to their excellent mechanical and physical properties, polyurethanes are used in a wide variety of areas. The field of polyurethane foams represents a particularly important market for the most varied types of polyurethanes.
- polyurethanes are understood to mean all reaction products starting from isocyanates, in particular from polyisocyanates, and corresponding isocyanate-reactive molecules. This also includes, inter alia, polyisocyanurates, polyureas and isocyanate or polyisocyanate reaction products containing allophanate, biuret, uretdione, uretimine or carbodiimide.
- Polyurethanes are now so widespread around the world that recycling these materials is becoming increasingly important. In the prior art, therefore, there are already different decomposition processes for recycling polyurethane waste.
- the well-known chemical processes such as hydrolysis, e.g. Amines are also produced as part of such polyurethane decomposition processes.
- di- and/or polyamines that result from the di- and/or isocyanates used in polyurethane production are key products that are returned to the value-added cycle through processing and conversion to isocyanates must.
- the invention relates to a process for preparing aromatic and/or aliphatic di- and/or polyisocyanates, comprising the following steps a) depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst which is selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200° C.
- di- and/or polyamines preferably comprising toluenediamine
- the method enables the provision of aromatic and / or aliphatic di- and / or polyisocyanates, such as in particular toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, which in turn can be used for the renewed production of polyurethane foam with a reduced content of dichlorobenzene compared to standard PU foam.
- aromatic and / or aliphatic di- and / or polyisocyanates such as in particular toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, which in turn can be used for the renewed production of polyurethane foam with a reduced content of dichlorobenzene compared to standard PU foam.
- This avoids the energy-intensive alkylation, nitration and hydrogenation of benzene, which is normally necessary to obtain, for example, toluene-2,4-diisocyanate.
- the invention opens up polyure
- isocyanates are produced in large quantities and are mainly used as starting materials for the production of polyurethanes. They are usually produced by reacting the corresponding amines, which can be obtained by refining petrochemical raw materials, with phosgene, phosgene being used in a stoichiometric excess. The reaction of the amines with the phosgene can take place either in the gas phase or in the liquid phase, and the reaction can be carried out batchwise or continuously (W. Siefken, Liebigs Ann. 562, 75-106 (1949)). Processes for preparing organic isocyanates from primary amines and phosgene have already been described several times, see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 4th ed. (1977),
- the resulting isocyanates comprise aromatic and/or aliphatic di- and/or polyisocyanates, such as methylenediphenyl diisocyanate (MDI - "monomeric MDI"), polymethylene-polyphenylene polyisocyanate (a mixture of MDI and higher homologues , PMDI, "polymeric MDI”), toluene diisocyanate (TDI) and/or isophorone diisocyanate (IPDI), in particular 2,4'-diphenylmethane diisocyanate and/or 2,2'-diphenylmethane diisocyanate and/or polyphenylpolymethylene polyisocyanate (crude MDI) and/or 2, 4-toluene diisocyanate and/or 2,6-toluene diisocyanate.
- MDI methylenediphenyl diisocyanate
- polymethylene-polyphenylene polyisocyanate a mixture of MDI and
- the process of this invention involves the depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising from 6 to 30 carbon atoms. atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200°C to form di- and/or polyamines.
- a catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising from 6 to 30 carbon atoms. atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200°C to form di- and/or polyamines.
- a particularly preferred variant, referred to here as preferred variant 1, of depolymerization by hydrolysis is described below.
- step a) using a base with a pKb value at 25 ° C from 1 to 10, preferably 1 to 8, more preferably 1 to 7, in particular 1, 5 to 6, and a catalyst selected from the group consisting of (i) quaternary ammonium salts containing an ammonium cation containing from 6 to 30 carbon atoms and (ii) organic sulfonate containing at least 7 carbon atoms.
- a base with a pKb value at 25 ° C from 1 to 10, preferably 1 to 8, more preferably 1 to 7, in particular 1, 5 to 6, and a catalyst selected from the group consisting of (i) quaternary ammonium salts containing an ammonium cation containing from 6 to 30 carbon atoms and (ii) organic sulfonate containing at least 7 carbon atoms.
- Preferred bases include an alkali metal cation and/or an ammonium cation.
- Preferred bases here are alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal carbonates, alkali metal silicates, alkali metal hydrogen carbonates, alkali metal acetates, alkali metal sulfites, ammonium hydroxides or mixtures of the aforementioned.
- Preferred alkali metals are Na, K or Li or mixtures of the aforementioned, in particular Na or K or mixtures thereof; preferred ammonium cation is NH 4 + .
- Particularly preferred bases are K2CO3, Na2SiC>3, NH4OH, K3PO4, or KOAc.
- the base is preferably used as a saturated alkaline solution in water, the weight ratio of saturated alkaline solution to PU being in the range of preferably 0.5 to 25, preferably 0.5 to 15, more preferably 1 to 10, in particular 2 to 7.
- Preferred quaternary ammonium salts have the general structure: Ri R2 R3 R4 NX with Ri, R2, R3 and R4 identical or different hydrocarbon groups selected from alkyl, aryl and/or arylalkyl, where Ri to R4 are preferably selected such that the sum of the carbon atoms of the quaternary ammonium cation is 6-14, preferably 7-14, more preferably 8-13.
- X is selected from halide, preferably chloride and/or bromide, bisulfate, alkyl sulfate, preferably methyl sulfate or ethyl sulfate, carbonate, bicarbonate or carboxylate, preferably acetate or hydroxide.
- Very particularly preferred quaternary ammonium salts are tributylmethylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, tributylmethylammonium chloride and/or trioctylmethylammonium methyl sulfate.
- the organic sulfonate containing at least 7 carbon atoms which can also be used as a catalyst preferably includes alkylaryl sulfonates, alpha-olefin sulfonates, petroleum sulfonates and/or naphthalene sulfonates.
- Preferred temperatures for the depolymerization are 80°C to 200°C, preferably 90°C to 180°C, more preferably 95°C to 170°C and in particular 100°C to 160°C.
- Preferred reaction times for the depolymerization are 1 minute to 14 hours, preferably 10 minutes to 12 hours, preferably 20 minutes to 11 hours and in particular 30 minutes to 10 hours.
- a preferred weight ratio of base to polyurethane is in the range from 0.01 to 50, preferably from 0.1 to 25, in particular from 0.5 to 20.
- a catalyst from the group of quaternary ammonium salts containing an ammonium cation with 6 to 14 carbon atoms if the ammonium cation does not contain a benzyl radical, or containing an ammonium cation with 6 to 12 carbon atoms if the ammonium cation contains a benzyl radical includes, takes place, there is a further preferred embodiment of the invention.
- Preferred bases here are alkali metal hydroxides, alkali metal oxides, alkaline earth metal hydroxides, alkali metal oxides or mixtures thereof.
- Preferred alkali metals are Na, K or Li or mixtures of the aforementioned, in particular Na or K or mixtures thereof;
- preferred alkaline earth metals are Be, Mg, Ca, Sr or Ba or mixtures thereof, preferably Mg or Ca or mixtures thereof.
- a very particularly preferred base is NaOH.
- Preferred quaternary ammonium salts have the general structure: Ri R 2 R 3 R 4 NX where Ri, R 2 , R 3 and R 4 are the same or different hydrocarbyl groups selected from alkyl, aryl and arylalkyl.
- X is selected from halide, preferably chloride and/or bromide, bisulfate, alkyl sulfate, preferably methyl sulfate or ethyl sulfate, carbonate, bicarbonate, carboxylate, preferably acetate or hydroxide.
- Particularly preferred quaternary ammonium salts here are benzyltrimethylammonium chloride or tributylmethylammonium chloride.
- Preferred temperatures for the depolymerization are 80°C to 200°C, preferably 90°C to 180°C, more preferably 95°C to 170°C and in particular 100°C to 160°C.
- Preferred reaction times for the depolymerization are 1 minute to 14 hours, preferably 10 minutes to 12 hours, preferably 20 minutes to 11 hours and in particular 30 minutes to 10 hours.
- a preferred weight ratio of base to polyurethane is in the range from 0.01 to 25, preferably 0.1 to 15, preferably 0.2 to 10, in particular 0.5 to 5.
- An alkaline solution comprising base and water, the concentration of the base preferably being greater than 5% by weight, preferably 5 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight %, more preferably 15 to 40% by weight, especially 20 to 40% by weight, based on the weight of the alkaline solution.
- the PU to be used in the PU depolymerization process can be any PU product, in particular it comprises a polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam, viscoelastic PU foam, HR PU foam, PU hypersoft Foam, semi-rigid PU foam, thermoformable PU foam and/or integral PU foam.
- a polyurethane foam preferably PU rigid foam, PU flexible foam, PU hot flexible foam, viscoelastic PU foam, HR PU foam, PU hypersoft Foam, semi-rigid PU foam, thermoformable PU foam and/or integral PU foam.
- di- and/or polyamines From the described depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst selected from the group comprising quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200° C di- and/or polyamines can thus be produced which, optionally after separating off other depolymerization products and reagents used for the depolymerization and optionally prior purification, are converted to di- and/or polyisocyanates by phosgenation.
- a catalyst selected from the group comprising quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms
- the di- and/or polyamines in question can be removed and, if necessary, purified as follows from the reaction mixture obtained via the depolymerization, which has optionally been pretreated by prior filtration, removal of the aqueous phase and/or distillation of volatile components: a) by distillation , preferably distillation under reduced pressure in the range from 0.01 mbar to 500 mbar, preferably 0.05 mbar to 350 mbar, more preferably 0.1 mbar to 200 mbar, particularly preferably 0.5 mbar to 100 mbar or b) by extraction with common organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, tetrahydrofuran, heptane or octane.
- common organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane
- Preferred, in the process recoverable aromatic di- and polyamines include methylenediphenyldiamine (MDA, or diamines of the diphenylmethane series) as isomers or as a mixture of isomers, polymethylenepolyphenylenepolyamine (PMDA, or polyamines of the diphenylmethane series), mixtures of methylenediphenyldiamine and
- Polymethylenepolyphenylenepolyamine (MDA, or also di- and polyamines of the diphenylmethane series), toluenediamine (TDA) as pure isomers or isomer mixtures of the isomers 2,4-toluenediamine and 2,6-toluenediamine, isomers of xylylenediamine (XDA), isomers of diaminobenzene, 2, 6-xylidine, 1,5-naphthylenediamine (1,5-NDA), particular preference is given to methylenediphenyldiamine (MDA, or else diamines of the diphenylmethane series) as an isomer mixture, polymethylenepolyphenylenepolyamine (PMDA, or else polyamines of the diphenylmethane series), mixtures of methylenediphenyldiamine and polymethylenepolyphenylenepolyamine ( MDA, or also di- and polyamines of the diphenylmethane series
- Preferred recoverable di- and/or triamines based on aliphatic or cycloaliphatic hydrocarbons having 2 to 18 carbon atoms include, for. 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane (HDA), 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2,2-dimethyl-1,5 -diaminopentane, 2-methyl-1,5-pentanediamine (MPDA), 2,4,4(or - 2,2,4)-trimethyl-1,6-diaminohexane (TMDA), 1,3- and 1,4 -Diaminocyclohexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA), 2,4-, or 2,6-diamino-1-methylcyclohexane (H6-T
- Bis(aminomethyl)cyclohexane bis(aminomethyl)norbornane (NBDA), 4,4'(and/or 2,4')-diaminodicyclohexylmethane, (cyclo)aliphatic triamines having up to 22 carbon atoms, such as triaminocyclohexane, tris( aminomethyl)cyclohexane, triaminomethylcyclohexane, 1,8-diamino-4-(aminomethyl)octane, 1,6,1-undecanetriamine, 1,7-diamino-4-(3-aminopropyl)heptane, 1,6-diamino-3 - (aminomethyl)-hexane and/or 1,3,5-tris(aminomethyl)-cyclohexane.
- NBDA bis(aminomethyl)norbornane
- the phosgenation of amines to form isocyanates is known per se. It can preferably be carried out as a gas-phase phosgenation of the amines previously converted into the gas phase together with gaseous phosgene at temperatures of about 300-400° C., the isocyanates being formed in the gaseous state. An excess of phosgene is always necessary to avoid the occurrence of undesirable side reactions between the isocyanates formed and the amines used as starting materials. Gas-phase phosgenation usually takes place as a continuous process. The development of adiabatic gas-phase phosgenation, as described, for example, in EP 1 616 857 A1, allows large amounts of energy to be saved compared with conventional phosgenation methods. In addition to the gas-phase phosgenation the process can be carried out in the liquid phase (liquid-phase phosgenation), which, however, has disadvantages due to the high solvent requirements.
- the present invention enables the provision of aromatic and/or aliphatic di- and/or polyisocyanates based on polyurethane depolymerization processes as described above.
- Preferred recycled aromatic di- and polyisocyanates accessible by the process according to the invention are methylenediphenyl diisocyanate (MDI, or also diisocyanates of the diphenylmethane series) as isomers or as a mixture of isomers, polymethylenepolyphenylene polyisocyanate (PMDI, or also polyisocyanates of
- Diphenylmethane series mixtures of methylenediphenyl diisocyanate and polymethylene polyphenylene polyisocyanate and/or toluene diisocyanate (TDI) as pure isomers or
- Preferred recycled aliphatic or cycloaliphatic di- or polyisocyanates accessible by the process according to the invention contain 2 to 18 carbon atoms and include 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (HDI), 1,8-octane diisocyanate, 1 ,9-nonane diisocyanate, 1,10-decane diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, 2-methyl-1,5-pentane diisocyanate (MPDI), 2,4,4(or 2,2,4)- Trimethyl-1,6-hexane diisocyanate (TMDI), 1,3- and 1,4-cyclohexane diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- or 2,6-cyclohexane
- the resulting di- and/or polyisocyanates can in turn be used to produce new polyurethanes therefrom.
- a further object of the present invention is therefore the use of a di- and/or polyisocyanate, obtained by a process according to the invention as described above, for the production of polyurethane, in particular PU foam.
- Such di- and/or polyisocyanates which have been obtained by a process according to the invention as described above are also referred to as recycled isocyanates for the purposes of this invention.
- the invention also makes it possible to use large amounts of appropriate recycling isocyanates, with no or only an insignificant reduction in the foam quality compared with a foam made from conventionally produced isocyanates.
- a further object of the invention is a process for the production of polyurethane, in particular PU foams, by reaction
- isocyanate component comprises recycled isocyanate obtained by a process according to the invention as described above.
- the proportion of recycled isocyanate according to the invention is more than 30% by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 95% by weight.
- the polyol component also comprises recycled polyol, obtained in particular by depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst which is selected from the group consisting of quaternary ammonium salts containing a ammonium cation comprising 6 to 30 carbon atoms and organic sulphonates containing at least 7 carbon atoms is selected as previously described.
- the method according to the invention using recycled isocyanate makes it possible to provide all known types of PU foam.
- the PU foam is a PU rigid foam, a PU flexible foam, a PU hot flexible foam (standard foam), a viscoelastic PU foam, an HR PU foam, a PU hypersoft foam semi-rigid PU foam, a thermoformable PU foam or a PU integral foam, preferably a PU hot flexible foam, HR PU foam, PU hypersoft foam or viscoelastic PU foam.
- PU hot flexible foam is most preferred.
- toluene diisocyanate as an isomer mixture of 2,4- and 2,6-toluene diisocyanate and/or methylene diphenyl diisocyanate (MDI) is used as the isocyanate component
- Isomer mixture of 4,4'-, 2,4'- and 2,2'-methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI) are used.
- TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and/or methylenediphenyl diisocyanate (MDI) as an isomer mixture of 4,4'-, 2,4'- and 2,2'- - Methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI) used.
- MDI methylenediphenyl diisocyanate
- CAde MDI or polymeric MDI polyphenylpolymethylene polyisocyanates
- toluene diisocyanate (TDI) as an isomer mixture of 2,4- and 2,6-toluene diisocyanate is preferably used as the isocyanate component.
- TDI is particularly preferably used in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI).
- Another preferred embodiment of the invention is the production of viscoelastic foams (also viscous foams). used as an isomer mixture of 4,4'-, 2,4'- and 2,2'-methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI).
- TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and/or in an isomer ratio of 65 to 35 (2,4-TDI to 2,6-TDI) and/or is particularly preferred Methylenediphenyl diisocyanate as a mixture of 4,4', 2,4'- and 2,2'-
- the aromatic polyisocyanates mentioned can be used individually or else in the form of their mixtures.
- Mixtures of TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and TDI in an isomer ratio of 65 to 35 (2,4-TDI to 2,6-TDI) are preferred for the production of viscoelastic polyurethane foams ) used or mixtures of TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and methylenediphenyl diisocyanate as Mixture of 4,4', 2,4'- and 2,2'-methylenediphenyl diisocyanates and
- Polyphenylpolymethylene polyisocyanate used.
- the PU foams can be produced in the usual manner and as described in the prior art. It is well known to those skilled in the art. A basic overview can be found e.g. B. in G. Oertel, Polyurethane Handbook, 2nd Edition, Hanser/Gardner Publications Inc., Cincinnati, Ohio, 1994, pp. 177-247. Further information on the usable starting materials, catalysts and auxiliaries and additives can be found, for example, in the Plastics Handbook, Volume 7, Polyurethane, Carl Hanser Verlag Kunststoff, 1st edition 1966, 2nd edition, 1983 and 3rd edition, 1993.
- Chain extenders cell openers, fragrances, cell coarseners, plasticizers, hardeners, aldehyde scavengers, additives for resistance of PU foams to hydrolysis, compatibilizers (emulsifiers), adhesion promoters, hydrophobing additives, flame lamination additives, additives for preventing cold flow, additives to reduce compression set , additives for adjusting the glass transition temperature, temperature-controlling additives and/or odor reducers, a further preferred embodiment of the invention is present.
- composition suitable for the production of polyurethane foam comprising at least one polyol component, at least one isocyanate component, catalyst, foam stabilizer, blowing agent, optional auxiliaries, the isocyanate component comprising recycled isocyanate, as described above.
- Preferred optional auxiliaries include surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers such as described in EP 2998333A1, fragrances, cell coarsening agents such as described in EP 2986661 B1, plasticizers, hardeners, additives for the prevention of Cold flow as described, for example, in DE 2507161C3, WO 2017029054A1, aldehyde scavengers as described, for example, in WO 2021/013607A1, additives for resistance of PU foams to hydrolysis, as described, for example, in US 2015/0148438A1, compatibilizers (emulsifiers), adhesion promoters, hydrophobing
- Additives such as described in EP 2292677A1, Compression set reducing additives, glass transition temperature adjusting additives, temperature controlling additives and/or odor reducing agents.
- the hard foam on the other hand, is permanently deformed.
- foam Various subgroups of foams that are preferred within the scope of the invention are described in more detail below, with the term “foam” being used synonymously for “foam” within the scope of this invention for the sake of simplicity.
- rigid polyurethane foam is understood in particular as meaning a foam according to DIN 7726:1982-05, which more preferably has a compressive strength according to DIN 53421:1984-06 of advantageously >20 kPa, preferably >80 kPa, preferably >100 kPa >150 kPa, particularly preferably >180 kPa.
- the rigid polyurethane foam advantageously has a closed cell content of more than 50%, preferably more than 80% and particularly preferably more than 90%.
- PU rigid foams are mostly used for insulation purposes.
- PU flexible foams are elastic and deformable and mostly open-celled. This allows the air to escape easily when compressed.
- the generic term of flexible PU foam includes in particular the following types of foam known to those skilled in the art, namely hot flexible PU foam (standard foam), PU cold foam (also highly elastic or high resilience foam), Hypersoft PU foam, viscoelastic PU soft foam and PU ester foams (made of polyester polyols).
- hot flexible PU foam standard foam
- PU cold foam also highly elastic or high resilience foam
- Hypersoft PU foam viscoelastic PU soft foam
- PU ester foams made of polyester polyols
- PU hot flexible foams can be made in particular by the rebound elasticity, also known as "ball rebound” (BR) or "resilience".
- BR rebound elasticity
- a method for determining the rebound resilience is described, for example, in DIN EN ISO 8307:2008-03.
- a steel ball with a specified mass is dropped onto the specimen from a certain height and the height of the rebound is then measured as a percentage of the dropping height.
- PU hot flexible foams have rebound values of preferably 1% to a maximum of 50%. In the case of PU cold flexible foams, the level of rebound is preferably in the range >50%.
- the high rebound resilience of PU cold flexible foams results from a relatively irregular cell size distribution. Another mechanical criterion is the SAG or comfort factor.
- PU hot flexible foams have a comfort factor of preferably ⁇ 2.5.
- the comfort factor is preferably > 2.5.
- polyether polyols which are particularly reactive towards isocyanates and have a high proportion of primary hydroxyl groups and number-average molar masses >4000 g/mol are used.
- PU hot flexible foams predominantly inert polyols with secondary OH groups and an average molar mass of ⁇ 4000 g/mol are usually used.
- cold molded foams which are used in automotive seat cushions, for example, represent a core application of PU cold foams.
- hypersoft PU foams which represent a subcategory of flexible PU foams.
- Hypersoft PU foams have compressive stresses determined according to DIN EN ISO 3386-1:1997 + A1:2010 of preferably ⁇ 2.0 kPa and have indentation hardnesses determined according to DIN EN ISO 2439:2009-05 of preferably ⁇ 80 N.
- Hypersoft PU foams can be manufactured using a variety of known methods: by using a so-called hypersoft polyol in combination with so-called standard polyols and/or by using a special manufacturing method in which carbon dioxide is added during the foaming process.
- Hypersoft PU foams Due to a pronounced open cell structure, Hypersoft PU foams have a high level of air permeability, promote the transport of moisture in application products and help to prevent heat build-up.
- the Hypersoft polyols used to produce Hypersoft PU foams are characterized in particular by a very high proportion of primary OH groups of more than 60%.
- a special class of flexible PU foams is that of viscoelastic PU foams (PU viscose foams), which are also preferred according to the invention. These are also under the name Memory foam is known and is characterized both by a low rebound elasticity according to DIN EN ISO 8307:2008-03 of preferably ⁇ 15% and by a slow, gradual recovery after compression (recovery time preferably 2 - 13 s).
- the glass transition temperature for viscoelastic PU foams is preferably shifted to a range from -20 to +15°C.
- a pneumatic effect must be distinguished from such "structural viscoelasticity" in open-cell viscoelastic PU foams, which is essentially based on the glass transition temperature of the polymer (also known as chemical viscofoams). In the latter case, there is a relatively closed cell structure (low porosity). Due to the low air permeability, the air only flows back in slowly after compression, which results in a slower recovery (also called pneumatic visco-foams). In many cases, both effects are combined in one visco-foam. PU visco-foams are used because of their energy - and sound-absorbing properties.
- a class of PU foams that is particularly important for applications in the automotive sector and that can be classified between those of rigid and flexible foams in terms of properties consists of semi-rigid (semi-flexible) PU foams. These are also preferred according to the invention. Like most PU foam systems, semi-flexible foam systems also use the isocyanate/water reaction and the resulting CO2 as a foaming agent. The rebound resilience is generally lower than that of classic flexible foams, especially cold foams. Semi-flexible foams are harder than conventional flexible foams. A characteristic feature of semi-flexible foams is their high number of open cells (preferably >90% of the cells). The densities of semi-flexible foams can be significantly higher than those of flexible and rigid foams.
- polyols which have two or more OH groups are preferably used as polyol components.
- Preferred polyols which can be used are all the polyether polyols and polyester polyols customarily used for the production of polyurethane systems, in particular polyurethane foams.
- Polyether polyols can, for. B. be obtained by reacting polyhydric alcohols or amines with alkylene oxides.
- Polyester polyols are preferably based on esters of polybasic carboxylic acids with polyhydric alcohols (mostly glycols).
- the polybasic carboxylic acids can be either aliphatic (e.g. adipic acid) or aromatic (e.g. phthalic acid or terephthalic acid).
- NOPs natural oil-based polyols
- PU foams in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices and has already been described many times in the production of polyurethane foams (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232).
- polyols from various manufacturers are now available on the market (WO 2004/020497, US 2006/0229375, WO 2009/058367).
- basic raw material e.g. soybean oil, palm oil or castor oil
- polyols with different properties result.
- the production of polyurethane foams from recycled polyols together with NOPs represents a preferred application of the invention.
- a further class of polyols which can optionally be used are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100:1 to 5:1, preferably 50:1 to 10:1.
- filler polyols represent yet another class of optionally usable polyols. These are characterized in that they contain solid organic fillers up to a solids content of 40% by weight or more in disperse distribution. For example, you can use:
- SAN polyols These are highly reactive polyols containing a dispersed styrene/acrylonitrile (SAN)-based copolymer.
- PHD Polyols These are highly reactive polyols containing polyurea particles in a dispersed form.
- PIPA Polyols These are highly reactive polyols containing polyurethane particles in dispersed form, prepared, for example, by the in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
- the solids content of the optional filler polyols which depending on the application can be between 5 and >40% by weight, based on the polyol, is responsible for improved cell opening, so that the polyol can be foamed in a controlled manner, especially with TDI, and there is no shrinkage of the foaming occurs.
- the solid thus acts as an essential process aid.
- Another function is to control the hardness via the solids content, since higher solids content causes the foam to be harder.
- polyols containing solids are significantly less inherently stable and therefore require physical stabilization in addition to chemical stabilization through the crosslinking reaction.
- Other polyols that can optionally be used are the so-called cell opener polyols.
- These are polyether polyols with a high ethylene oxide content, preferably at least 40% by weight, in particular from 50 to 100% by weight, based on the alkylene oxide content.
- a ratio of isocyanate component to polyol component that is preferred in the context of this invention, expressed as an index, is in the range from 10 to 1000, preferably 40 to 350.
- This index describes the ratio of the amount of isocyanate actually used to the theoretically required amount of isocyanate, corresponding to a stoichiometric ratio of isocyanate Groups to isocyanate-reactive groups (e.g. OH groups, NH groups), multiplied by 100.
- An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
- the isocyanate component necessarily contains recycled isocyanate obtained by a process according to the invention as described above.
- the term recycled isocyanates includes di- and/or polyisocyanates obtained by a process according to the invention, as described above. It corresponds to a preferred embodiment of the invention if the proportion of recycled isocyanate, based on the total isocyanate component used, is more than 30 % by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 95% by weight.
- One or more isocyanates which have two or more isocyanate functions are preferably used as isocyanate components, the isocyanate component comprising recycled diisocyanate obtainable according to the invention.
- Any isocyanates, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se, can be used as optionally additionally usable isocyanates in the process according to the invention.
- Suitable isocyanates for the purposes of this invention have two or more isocyanate functions.
- Suitable isocyanates for the purposes of this invention are preferably all polyfunctional organic isocyanates, such as diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and/or isophorone diisocyanate (IPDI).
- MDI diphenylmethane diisocyanate
- TDI toluene diisocyanate
- HMDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- the mixture of MDI and higher-condensed analogues with an average functionality of 2 to 4, known as “polymeric MDI” (“crude MDI” or polyphenylpolymethylene polyisocyanate), can also preferably be used.
- MDI prepolymers are also particularly suitable. Examples of particularly suitable isocyanates are listed, for example, in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, to which reference is made here in its entirety.
- Suitable catalysts which can be used in the process according to the invention for producing PU foam are preferably substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the dimerization or trimerization of the isocyanate.
- the catalyst used is selected from triethylenediamine, 1,4-diazabicyclo[2.2.2]octane-2-methanol, diethanolamine, N-[2-[2-[2-]
- X includes oxygen, nitrogen, hydroxyl, amines of structure (NR m or NR m R lv ) or urea groups (N(R V )C(O)N(R VI ) or N(R V ")C(O)NR VI RV ”)
- Y includes amines NR VIII R IX or ethers OR lx
- R UI include identical or different linear or cyclic, aliphatic or aromatic hydrocarbons with 1-8 carbon atoms which are optionally functionalized with an OH group; and/or comprise hydrogen
- R x includes identical or different radicals consisting of hydrogen and/or linear, branched or cyclic aliphatic or aromatic hydrocarbons with 1-18 carbon atoms, which can be substituted with 0-1 hydroxyl groups and 0-1 NH 2 groups.
- Z includes oxygen, NRx or CH2.
- metal compounds of the metals Sn, Bi, Zn, Al or K especially Sn, Zn or Bi.
- the metal compounds can be divided into the subgroups of organometallic compounds, organometallic Classify salts, organic metal salts and inorganic metal salts, which are explained below.
- organometallic or organometallic compounds includes, in particular, the use of metal-containing compounds that have a direct carbon-metal bond, here also as organometallic compounds (e.g. organotin compounds) or organometallic or organometallic compounds (e.g. organotin compounds). ) designated.
- organometallic or organometallic salts includes in particular the use of organometallic or organometallic compounds with a salt character, i.e. ionic compounds in which either the anion or cation is of an organometallic nature (e.g. organotin oxides, organotin chlorides or organotin -carboxylates).
- organic metal salts includes in particular the use of metal-containing compounds that do not have a direct carbon-metal bond and are at the same time metal salts in which either the anion or the cation is an organic compound (e.g. tin(II )-carboxylates).
- organic metal salts includes in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, e.g. metal chlorides (e.g. tin(II) chloride).
- Suitable organic and organometallic metal salts that can be used preferably contain alcoholate, mercaptate or carboxylate anions such as, for example, acetate, 2-ethylhexanoate, octanoate, isononanoate, decanoate, neodecanoate, ricinoleate, laurate and/or oleate, particularly preferably 2-ethylhexanoate, ricinoleate , neodecanoate or isononanoate.
- Suitable metal-containing catalysts that can be used are generally preferably selected such that they have no objectionable intrinsic odor, are essentially toxicologically harmless and that the resulting polyurethane systems, in particular polyurethane foams, have the lowest possible catalyst-related emissions. It may be preferred to combine one or more metal compounds with one or more amine catalysts of formula (1a) and/or (1b).
- organometallic salts such as dibutyltin dilaurate.
- Suitable water contents in the process according to the invention depend on whether or not physical blowing agents are used in addition to the water. In the case of purely water-blown foams, the values are preferably from 1 to 20 pphp, but if other blowing agents are also used, the amount used is usually reduced to, for example, 0 or, for example, 0.1 to 5 pphp. In order to achieve high foam density, preferably neither water nor other blowing agents are used.
- Suitable physical blowing agents that can optionally be used in the context of this invention are gases, for example liquefied CO2, and volatile liquids, for example hydrocarbons with 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, but also olefinic fluorocarbons such as HHO 1233zd or HH01336mzzZ, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
- ketones e.g. acetone
- aldehydes e.g. methylal
- compositions of the invention may contain one or more stabilizers.
- stabilizers are in particular silicon compounds having carbon atoms, preferably selected from the polysiloxanes, polydimethylsiloxanes, organomodified polysiloxanes, polyether-modified polysiloxanes and polyether-polysiloxane copolymers. Preferred silicon compounds are described by formula (1c):
- R 5 independently the same or different alkyl radicals consisting of 1 to 16 carbon atoms, aryl radicals having 6 to 16 carbon atoms or hydrogen, preferably from the group of alkyl radicals having 1 to 6 carbon atoms or aryl radicals having 6 to 10 carbon atoms or hydrogen, particularly preferably methyl or hydrogen.
- R 1 identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms or hydrogen or -OR 6 , preferably methyl, ethyl, octyl, dodecyl, phenyl or hydrogen, particularly preferred methyl or phenyl.
- R 2 independently identical or different polyethers obtainable through the
- R 7 divalent organic radical, preferably divalent organic alkyl or aryl radical optionally substituted with -OR 6 , more preferably a divalent organic radical of the type C P H 2p .
- R 3 identical or different radicals selected from the group of saturated or unsaturated alkyl radicals potentially substituted with heteroatoms, preferably identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms potentially substituted with Halogen atoms, particularly preferably methyl, vinyl, chloropropyl or phenyl.
- R 6 identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms or hydrogen, preferably saturated or unsaturated alkyl radicals having 1 to 8 carbon atoms or hydrogen, methyl, ethyl being particularly preferred , isopropyl or hydrogen.
- R 8 identical or different radicals selected from the group of alkyl radicals with 1 to 18 carbon atoms, potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms, aryl radicals with 6 - 18 carbon atoms, potentially substituted with ether functions, or hydrogen, preferably alkyl radicals with 1 to 12 carbon atoms potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms or aryl radicals having 6 to 12 carbon atoms potentially substituted with ether functions, or hydrogen, more preferably methyl, ethyl, benzyl or hydrogen.
- R 9 same or different radicals selected from the group hydrogen, alkyl, -C(0)-R 11 , -C(0)0-R 11 or -C(0)NHR 11 , saturated or unsaturated, optionally substituted with Heteroatoms, preferably hydrogen or alkyl radicals having 1 to 8 carbon atoms or acetyl, particularly preferably hydrogen, acetyl, methyl or butyl.
- R 10 identical or different radicals selected from the group of saturated or unsaturated alkyl radicals or aryl radicals, potentially substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, preferably saturated or unsaturated alkyl radicals with 1 to 18 Carbon atoms or aryl radicals with 6 - 18 carbon atoms optionally substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, more preferably saturated or unsaturated alkyl radicals with 1 to 18 carbon atoms or aryl radicals with 6 - 18
- R 11 identical or different radicals selected from the group consisting of alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms, preferably saturated or unsaturated alkyl radicals having 1 to 8 carbon atoms or aryl radicals
- the foam stabilizers of the formula (1c) can be used in PU systems, preferably mixed in organic solvents such as, for example, dipropylene glycol, polyether alcohols or polyether diols.
- organic solvents such as, for example, dipropylene glycol, polyether alcohols or polyether diols.
- a compatibilizer can preferably also be used. This can be selected from the group of aliphatic or aromatic hydrocarbons, particularly preferably aliphatic polyethers or polyesters.
- the substances mentioned in the prior art can preferably be used as silicon compounds having one or more carbon atoms.
- Those Si compounds which are particularly suitable for the particular type of foam are preferably used.
- Suitable siloxanes are described, for example, in the following documents: EP 0839852, EP 1544235, DE 102004001408, WO 2005/118668, US 2007/0072951, DE 2533074, EP 1537159 EP 533202, US 3933695, EP 0780414, DE 4239054, DE 4229402, EP 867465.
- the Si compounds can be prepared as described in the prior art. Suitable examples are e.g. e.g. in US 4147847, EP 0493836 and US 4855379.
- foam stabilizers in particular silicon compounds
- polyol components Preferably, from 0.00001 to 20 parts by mass of foam stabilizers, in particular silicon compounds, can be used per 100 parts by mass of polyol components.
- blowing agents preferably water to form CO2 and, if necessary, other physical blowing agents
- Flame retardants buffer substances, surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers as described, for example, in EP 2998333A1, nucleating agents, thickeners, fragrances, cell coarsening agents, as described, for example, in EP 2986661 B1, plasticizers, hardeners, additives for preventing cold flow as described, for example, in DE 2507161C3, WO 2017029054A1, aldehyde scavengers as described, for example, in WO 2021/013607 A1, additives for the resistance of PU foams to hydrolysis, as described, for example, in US
- compatibilizers emulsifiers
- adhesion promoters adhesion promoters
- hydrophobing additives flame lamination additives as described, for example, in EP 2292677B1
- compression set-reducing additives odor reducers and/or additional catalytically active substances, in particular as defined above.
- Crosslinkers that can be used as an option and chain extenders that can be used as an option are low molecular weight, polyfunctional compounds that are reactive toward isocyanates.
- hydroxyl- or amine-terminated substances such as glycerol, neopentyl glycol, dipropylene glycol, sugar compounds, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane are suitable.
- Crosslinkers that can also be used are polyethoxylated and/or polypropoxylated glycerol or sugar compounds whose number-average molecular weight is below 1500 g/mol.
- the optional use concentration is preferably between 0.1 and 5 parts, based on 100 parts of polyol, but can also deviate from this depending on the formulation.
- crude MDI for foam molding, this also takes on a crosslinking function.
- the content of low-molecular crosslinkers can therefore be correspondingly reduced as the amount of crude MDI increases.
- Suitable optional stabilizers against oxidative degradation are preferably all common free-radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators).
- Compounds of the following classes of substances, or classes of substances containing the following functional groups can preferably be used: 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acids and benzoates, phenols, in particular containing tert-butyl and/or methyl substituents on the aromatic compound, Benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones.
- Suitable optional flame retardants for the purposes of this invention are all substances which are considered suitable according to the prior art.
- Preferred flame retardants are, for example, liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, e.g. tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloroisopropyl) phosphate ( TDCPP) and tris(2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g.
- TEP triethyl phosphate
- TDP triethyl phosphate
- TCPP tris(1-chloro-2-propyl) phosphate
- TDCPP tris(1,3-dichloroisopropyl) phosphate
- TCEP tris(2-chloroethyl) phosphat
- DMMP dimethyl methane phosphonate
- DMPP dimethyl propane phosphonate
- oligomers ethyl ethylene phosphates or solids such as ammonium polyphosphate (APP) and red phosphorus.
- halogenated compounds for example halogenated polyols, and solids such as expandable graphite and melamine are also suitable as flame retardants.
- polyurethane foam can be produced by the process according to the invention.
- polyurethane is to be understood in particular as a generic term for a polymer made from di- or polyisocyanates and polyols or other species that are reactive towards isocyanate, such as amines, for example, where the urethane bond does not have to be the exclusive or predominant type of bond.
- polyisocyanurates and polyureas are also expressly included.
- polyurethane foams according to the invention can be carried out by any method familiar to the person skilled in the art, for example by hand mixing or preferably with the aid of high-pressure or low-pressure foaming machines.
- the process according to the invention can be carried out continuously or batchwise.
- a discontinuous implementation of the method is preferred in the production of molded foams, refrigerators, shoe soles or panels.
- a continuous procedure is preferred in the production of insulating panels, metal composite elements, blocks or spray processes.
- Another object of the present invention is a polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam (standard foam), viscoelastic PU foam, HR PU foam, PU hypersoft foam, semi-rigid PU foam, thermoformable PU foam or PU integral foam, preferably PU hot flexible foam, HR PU foam, PU hypersoft foam or viscoelastic PU foam, produced according to a method according to the invention as described above.
- PU hot flexible foams are most preferred.
- a very particularly preferred flexible polyurethane foam for the purposes of this invention has the following composition in particular:
- blowing agents 0 to 130 Flame retardants 0 to 70 Fillers 0 to 150
- Other additives 0 to 20
- Isocyanate including recycled isocyanate Isocyanate index: greater than 50
- the polyurethane foams according to the invention can, for. B. as refrigerator insulation, insulating board, sandwich element, pipe insulation, spray foam, 1 & 1.5 component can foam (a 1.5 component can foam is a foam that is produced by destroying a container in the can), imitation wood, model foam , packaging foam, mattress, furniture pad, automotive seat pad, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant, adhesive, binder, paint or as a coating or to manufacture related products be used.
- a 1.5 component can foam is a foam that is produced by destroying a container in the can
- imitation wood, model foam packaging foam, mattress, furniture pad, automotive seat pad, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant, adhesive, binder, paint or as a coating or to manufacture related products be used.
- the recycling toluene diisocyanate according to the invention was obtained by the hydrolysis of polyurethane in the presence of a saturated K2C03 solution and tetrabutylammonium hydrogen sulfate as catalyst and subsequent phosgenation of the isolated toluenediamine mixture:
- a Parr reactor (Parr Instrumental Company) equipped with a PTFE inner vessel and a mechanical stirrer was charged with 25 g of compressed foam pieces (ca. 1 cm ⁇ 1 cm).
- the polyurethane foam used was according to the one listed below
- Formulation 1 prepared. Then 75 g of saturated K 2 CC>3 solution (pKb value 3.67 at 25 °C) were added. The catalyst tetrabutylammonium hydrogen sulfate was then added at 5% by weight, based on the mass of the reaction mixture. The reactor was sealed and the reaction mixture was heated to an internal temperature of 150°C for 14 hours. Upon completion of the 14 hours, heating was discontinued and the reaction mixture was cooled to room temperature. After opening the reactor, the reaction mixture was transferred to a round bottom flask. The water was removed via rotary evaporation and the remaining reaction mixture extracted with cyclohexane and then filtered. The solid which was filtered off was extracted with toluene and the extraction solution obtained was dried.
- the toluenediamine was obtained as a mixture of isomers.
- To convert to the isocyanate 24 g of the toluenediamine were dissolved in 1.2 L of toluene. Then 250 ml_ of a 0.157 molar solution of triphosgene in toluene were added dropwise. After the addition was complete, the reaction mixture was heated to 110° C. and stirred under reflux at this temperature for 2 h. Then the reaction mixture was cooled to room temperature and filtered. After removing the solvent via rotary evaporation, the toluene diisocyanate isomer mixture was obtained. The process was repeated to provide a large enough amount of recycled toluene diisocyanate for the foaming experiments.
- 1.0 part (1.0 pphp) of a component means 1 g of this substance per 100 g of polyol.
- Table 1 Formulation for the production of PU hot-cure flexible foams.
- Polyol standard polyether polyol Arcol® 1104 available from Covestro, this is a glycerol-based polyether polyol with an OH number of 56 mg KOH/g and a number-average molar mass of 3000 g/mol.
- KOSMOS® T9 available from Evonik Industries: tin(II) salt of 2-ethylhexanoic acid.
- DABCO ® DMEA dimethylethanolamine, available from Evonik Industries. Amine catalyst for the production of polyurethane foams
- Toluene diisocyanate Desmodur® T 80 conventional toluene diisocyanate, available from Covestro, is a T 80 toluene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) with a viscosity of 3 mPa ⁇ s , 48% NCO and a functionality of 2 or recycling toluene diisocyanate according to the invention.
- the polyurethane foams were produced in the laboratory as so-called hand foams.
- the foams were produced according to the following information at 22° C. and 762 mm Hg air pressure.
- 100 g of polyol were used in each case.
- the other formulation components were converted accordingly.
- 1.0 part (1.0 pphp) of a component meant 1 g of this substance per 100 g of polyol.
- the tin catalyst tin(II) 2-ethylhexanoate, polyol, the water, the amine catalysts and the respective foam stabilizer were placed in a paper cup and mixed for 60 s with a disc stirrer at 1000 rpm. After the initial stirring, the isocyanate was added and incorporated with the same stirrer for 7 s at 2500 rpm and immediately transferred to a paper-lined box (19 cm x 19 cm base and 19 cm height). After pouring, the foam rose in the foaming box. Ideally, the foam blew off when the maximum rise height was reached and then sagged back slightly. The cell membranes of the foam bubbles opened up and an open-pored cell structure of the foam was obtained.
- Foam height is the height of the free-rising foam formed after 3 minutes. Foam height is reported in centimeters (cm). c) rise time
- the air permeability of the foam was determined based on DIN EN ISO 4638:1993-07 by measuring the dynamic pressure on the foam. The back pressure measured was given in mm of water column, with the lower back pressure values then characterizing the more open foam. The values were measured in the range from 0 to 300 mm water column.
- the dynamic pressure was measured using an apparatus comprising a nitrogen source, reducing valve with manometer, flow control screw, washing bottle, flow meter, T-piece, support nozzle and a scaled glass tube filled with water.
- the support nozzle has an edge length of 100 ⁇ 100 mm, a weight of 800 g, a clear width of the outlet opening of 5 mm, a clear width of the lower support ring of 20 mm and an outer diameter of the lower support ring of 30 mm.
- the measurement is carried out by setting the nitrogen pre-pressure to 1 bar using the reducing valve and adjusting the flow rate to 480 l/h.
- the amount of water is set in the graduated glass tube in such a way that no pressure difference can be built up and read.
- the contact nozzle is placed congruently at the corners of the test specimen edges and once at the (estimated) center of the test specimen (each on the side with the largest surface). It is read when a constant back pressure has been established.
- the evaluation is carried out by averaging over the five measured values obtained.
- the recycling toluene diisocyanate according to the invention is tested in formulation I, Table 1 in comparison with the conventional toluene diisocyanate T 80.
- Table 2 shows the results of the performance tests for the use of the various isocyanates.
- Table 2 Foaming results for the hot flexible PU foams, produced according to Formulation 1, Table 1 using the recycling diisocyanate according to the invention and the conventional toluene diisocyanate Desmodur T 80 from Covestro.
- the results in Table 2 show that the recycling toluene diisocyanate according to the invention can be used at 30% as the isocyanate component, with comparable foaming behavior analogous to that observed when using 100% of the conventional toluene diisocyanate Desmodur® T 80. In particular, the rise time remains almost unchanged.
- the foam height of foam #2 is only slightly below that of reference foam #1 with Desmodur® T80.
- the foam bodies #1 and #2 obtained have comparable physical foam properties with regard to porosity and cell number.
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Abstract
The invention relates to a process for producing aromatic and/or aliphatic diisocyanates, comprising the following steps: a) depolymerising a polyurethane by hydrolysis in the presence of a base and a catalyst, which is selected from the group consisting of quaternary ammonium salts containing an ammonium cation having (6) to (30) carbon atoms and organic sulfonates containing at least (7) carbon atoms, at temperatures preferably below 200°C to produce di- and/or polyamines; b) separating the di- and/or polyamines recovered from step a) from the reaction mixture by extraction, distillation and/or other separation processes; c) phosgenating the di- and/or polyamines obtained from step b) to form di- and/or polyisocyanates, wherein in the phosgenation step c), di- and/or polyamines which do not originate from process step a) are also optionally added.
Description
Gewinnung von Di- und/oder Polyisocyanaten aus PU-Depolymerisationsprozessen Recovery of di- and/or polyisocyanates from PU depolymerization processes
Die Erfindung liegt auf dem Gebiet der Di- und/oder Polyisocyanate, der Polyurethane und des Polyurethanrecyclings. Insbesondere wird ein Verfahren zur Herstellung aromatischer und/oder aliphatischer Di- und/oder Polyisocyanate beschrieben, welches von der Depolymerisation eines Polyurethans durch Hydrolyse ausgeht. The invention is in the field of di- and/or polyisocyanates, polyurethanes and polyurethane recycling. In particular, a process for preparing aromatic and/or aliphatic di- and/or polyisocyanates is described, which starts from the depolymerization of a polyurethane by hydrolysis.
Polyurethane finden aufgrund ihrer hervorragenden mechanischen und physikalischen Eigenschaften in den verschiedensten Bereichen Verwendung. Einen besonders wichtigen Markt für verschiedenste Typen von Polyurethanen stellt der Bereich der Polyurethanschäume dar. Als Polyurethane (PU) werden im Sinne dieser Erfindung alle Reaktionsprodukte ausgehend von Iso- cyanaten, insbesondere von Polyisocyanaten, und entsprechend isocyanat-reaktiven Molekülen verstanden. Dies umfasst unter anderem auch Polyisocyanurate, Polyharnstoffe sowie Allophanat-, Biuret-, Uretdion-, Uretimin- oder Carbodiimid-enthaltende Isocyanat- oder Polyisocyanat- Reaktionsprodukte. Due to their excellent mechanical and physical properties, polyurethanes are used in a wide variety of areas. The field of polyurethane foams represents a particularly important market for the most varied types of polyurethanes. In the context of this invention, polyurethanes (PU) are understood to mean all reaction products starting from isocyanates, in particular from polyisocyanates, and corresponding isocyanate-reactive molecules. This also includes, inter alia, polyisocyanurates, polyureas and isocyanate or polyisocyanate reaction products containing allophanate, biuret, uretdione, uretimine or carbodiimide.
Polyurethane sind weltweit inzwischen so weit verbreitet, dass auch bei diesen Stoffen eine Wiederverwertung immer wichtiger wird. Im Stand der Technik existieren daher bereits unterschiedliche Zersetzungsverfahren zur Verwertung von Polyurethan-Abfällen. Die bekannten chemischen Verfahren wie die Hydrolyse z.B. beschrieben in US 5,208,379, Glykolyse, Acidolyse, Aminolyse, Hydrogenolyse, Solvolyse und ähnliche Verfahren zielen auf eine Depolymerisation auf molekularer Ebene ab. Im Rahmen von solchen Polyurethan-Zersetzungsprozessen fallen auch Amine an.Polyurethanes are now so widespread around the world that recycling these materials is becoming increasingly important. In the prior art, therefore, there are already different decomposition processes for recycling polyurethane waste. The well-known chemical processes such as hydrolysis, e.g. Amines are also produced as part of such polyurethane decomposition processes.
Es besteht ein grundsätzlicher Bedarf daran, entsprechende Amine, welche aus Polyurethan- Zersetzungsprozessen resultieren, optimal zu verwerten. Dabei sind insbesondere die Di- und/oder Polyamine, die aus den bei der Polyurethan-Herstellung eingesetzten Di- und/oder Isocyanaten hervorgehen (z.B. Toluoldiamin bei PU aus Toluoldiisocyanat), entscheidende Produkte, die dem Wertschöpfungszyklus durch Aufbereitung und Umsetzung zu Isocyanaten zurückgeführt werden sollen. Insbesondere wird angestrebt, aus solchen Di- und/oder Polyaminen aromatische und/oder aliphatische Di- und/oder Polyisocyanate zu gewinnen, deren hohe Qualität die Wiederverwendung bei erneuter Polyurethan-Herstellung zulässt. Dieses zu verwirklichen, war die Aufgabe der vorliegenden Erfindung. There is a fundamental need to optimally utilize corresponding amines which result from polyurethane decomposition processes. In particular, the di- and/or polyamines that result from the di- and/or isocyanates used in polyurethane production (e.g. toluene diamine in PU from toluene diisocyanate) are key products that are returned to the value-added cycle through processing and conversion to isocyanates must. In particular, efforts are being made to obtain aromatic and/or aliphatic di- and/or polyisocyanates from such di- and/or polyamines, the high quality of which allows them to be reused in renewed polyurethane production. Realizing this was the task of the present invention.
Diese Aufgabe wird gelöst vom Gegenstand der Erfindung. Gegenstand der Erfindung ist ein Verfahren zur Herstellung von aromatischen und/oder aliphatischen Di- und/oder Polyisocyanaten, umfassend folgende Schritte a) Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators welcher aus der Gruppe bestehend aus quartären Ammoniumsalzen enthaltend ein Ammonium Kation umfassend 6 bis 30 Kohlenstoff-Atome und organischen Sulfonaten enthaltend wenigstens 7 Kohlenstoffatome gewählt ist, bei Temperaturen vorzugsweise unter 200 °C unter Erzeugung von Di- und/oder Polyaminen, vorzugsweise umfassend Toluoldiamin, b) Abtrennung der aus Schritt a) gewonnen Di- und/oder Polyamine, vorzugsweise umfassend Toluoldiamin, von der Reaktionsmischung durch Extraktion, Destillation und/oder andere
Trennverfahren, c) Phosgenierung der aus Schritt b) erhaltenen Di- und/oder Polyamine zu Di- und/oder Polyisocyanaten, wobei in dem Phosgenierungsschritt c) optional auch Di- und/oder Polyamine hinzugefügt werden können, welche nicht aus dem Verfahrensschritt a) stammen. Das Verfahren ermöglicht die Bereitstellung von aromatischen und/oder aliphatischen Di- und/oder Polyisocyanaten, wie insbesondere Toluol-2,4-diisocyanat und Toluol-2,6-diisocyanat, welche wiederum zur erneuten Herstellung von Polyurethanschaum verwendet werden können und zwar mit einem reduzierten Gehalt an Dichlorbenzol im Vergleich zu Standard PU-Schaum. Dabei werden die energieintensive Alkylierung, Nitrierung und Hydrierung von Benzol vermieden, welche normalerweise nötig sind, um z.B. zu Toluol-2,4-diisocyanat zu gelangen. Ferner werden durch die Erfindung Polyurethanabfälle als nachhaltige Rohstoffquelle für Di- und/oder Polyisocyanate erschlossen. This object is solved by the subject matter of the invention. The invention relates to a process for preparing aromatic and/or aliphatic di- and/or polyisocyanates, comprising the following steps a) depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst which is selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200° C. to produce di- and/or polyamines, preferably comprising toluenediamine, b) separating off the di- and /or polyamines, preferably comprising toluenediamine, from the reaction mixture by extraction, distillation and/or others Separation process, c) phosgenation of the di- and/or polyamines obtained from step b) to form di- and/or polyisocyanates, it being possible in the phosgenation step c) to optionally also add di- and/or polyamines which are not from process step a) come. The method enables the provision of aromatic and / or aliphatic di- and / or polyisocyanates, such as in particular toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, which in turn can be used for the renewed production of polyurethane foam with a reduced content of dichlorobenzene compared to standard PU foam. This avoids the energy-intensive alkylation, nitration and hydrogenation of benzene, which is normally necessary to obtain, for example, toluene-2,4-diisocyanate. Furthermore, the invention opens up polyurethane waste as a sustainable source of raw materials for di- and/or polyisocyanates.
Konventionelle Isocyanate werden in großen Mengen hergestellt und dienen hauptsächlich als Ausgangsstoffe zur Herstellung von Polyurethanen. Ihre Herstellung erfolgt zumeist durch Umsetzung der entsprechenden durch Veredlung petrochemischer Rohstoffe zugänglichen Amine mit Phosgen, wobei Phosgen im stöchiometrischen Überschuss eingesetzt wird. Die Umsetzung der Amine mit dem Phosgen kann sowohl in der Gasphase als auch in der Flüssigphase erfolgen, wobei die Reaktion diskontinuierlich oder kontinuierlich durchgeführt werden kann (W. Siefken, Liebigs Ann. 562, 75 - 106 (1949)). Verfahren zur Herstellung von organischen Isocyanaten aus primären Aminen und Phosgen sind bereits mehrfach beschrieben worden, siehe beispielsweise Ullmanns Encyklopädie der technischen Chemie, 4. Aufl. (1977),Conventional isocyanates are produced in large quantities and are mainly used as starting materials for the production of polyurethanes. They are usually produced by reacting the corresponding amines, which can be obtained by refining petrochemical raw materials, with phosgene, phosgene being used in a stoichiometric excess. The reaction of the amines with the phosgene can take place either in the gas phase or in the liquid phase, and the reaction can be carried out batchwise or continuously (W. Siefken, Liebigs Ann. 562, 75-106 (1949)). Processes for preparing organic isocyanates from primary amines and phosgene have already been described several times, see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 4th ed. (1977),
Band 13, S. 351 bis 353 sowie G. Wegener et. al. Applied Catalysis A: General 221 (2001), S. 303 - 335, Elsevier Science B.V. Es kommen dabei sowohl aromatische Isocyanate wie beispielsweise Methylendiphenyldiisocyanat (MDI - „monomeres MDI"), Polymethylen-Polyphenylen-Polyisocyanat (ein Gemisch aus MDI und höheren Homologen, PMDI, „polymeres MDI") oderToluoldiisocyanat (TDI) als auch aliphatische Isocyanate wie z. B. Hexamethylendiisocyanat (HDI) oder Isophorondiisocyanat (IPDI) weltweit zum Einsatz. Volume 13, pp. 351 to 353 and G. Wegener et. al. Applied Catalysis A: General 221 (2001), pp. 303-335, Elsevier Science B.V. There are both aromatic isocyanates such as methylenediphenyl diisocyanate (MDI - "monomeric MDI"), polymethylene-polyphenylene polyisocyanate (a mixture of MDI and higher homologues, PMDI, "polymeric MDI") or toluene diisocyanate (TDI) and aliphatic isocyanates such. B. hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) used worldwide.
Es entspricht einer bevorzugten Ausführungsform der Erfindung, wenn die resultierenden Isocyanate aromatische und/oder aliphatische Di- und/oder Polyisocyanate umfassen, wie z.B. Methylendiphenyldiisocyanat (MDI - „monomeres MDI"), Polymethylen-Polyphenylen-Polyisocyanat (ein Gemisch aus MDI und höheren Homologen, PMDI, „polymeres MDI"), Toluoldiisocyanat (TDI) und/oder Isophorondiisocyanat (IPDI), insbesondere 2,4‘-Diphenylmethandiisocyanat und/oder 2, 2‘- Diphenylmethandiisocyanat und/oder Polyphenylpolymethylenpolyisocyanat (crude MDI) und/oder 2,4-Toluoldiisocyanat und/oder 2,6-Toluoldiisocyanat. Toluol-2,4-diisocyanat und/oder Toluol-2,6-diisocyanat sind am meisten bevorzugt. It corresponds to a preferred embodiment of the invention when the resulting isocyanates comprise aromatic and/or aliphatic di- and/or polyisocyanates, such as methylenediphenyl diisocyanate (MDI - "monomeric MDI"), polymethylene-polyphenylene polyisocyanate (a mixture of MDI and higher homologues , PMDI, "polymeric MDI"), toluene diisocyanate (TDI) and/or isophorone diisocyanate (IPDI), in particular 2,4'-diphenylmethane diisocyanate and/or 2,2'-diphenylmethane diisocyanate and/or polyphenylpolymethylene polyisocyanate (crude MDI) and/or 2, 4-toluene diisocyanate and/or 2,6-toluene diisocyanate. Toluene 2,4-diisocyanate and/or toluene 2,6-diisocyanate are most preferred.
Das erfindungsgemäße Verfahren beinhaltet die Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators, welcher aus der Gruppe bestehend aus quartären Ammoniumsalzen enthaltend ein Ammonium Kation umfassend 6 bis 30 Kohlenstoff-
Atome und organischen Sulfonaten enthaltend wenigstens 7 Kohlenstoffatome gewählt ist, bei Temperaturen vorzugsweise unter 200 °C unter Erzeugung von Di- und/oder Polyaminen. The process of this invention involves the depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising from 6 to 30 carbon atoms. atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200°C to form di- and/or polyamines.
Entsprechende und bevorzugte Hydrolyseprozesse von PU-Materialien werden z.B. beschrieben in den noch unveröffentlichten europäischen Patentanmeldungen mit den Aktenzeichen 20192354.7 oder 20192364.6. Corresponding and preferred hydrolysis processes of PU materials are described, for example, in the as yet unpublished European patent applications with file numbers 20192354.7 or 20192364.6.
Im Folgenden wird eine besonders bevorzugte Variante, hier bevorzugte Variante 1 genannt, der Depolymerisation durch Hydrolyse beschrieben. A particularly preferred variant, referred to here as preferred variant 1, of depolymerization by hydrolysis is described below.
Insbesondere ist es bevorzugt, wenn die Depolymerisation des Polyurethans in Schritt a) unter Einsatz einer Base mit einem pKb Wert bei 25 °C von 1 bis 10, vorzugsweise 1 bis 8, weiter bevorzugt 1 bis 7, insbesondere 1 ,5 bis 6, sowie eines Katalysators ausgewählt aus der Gruppe bestehend aus (i) quartären Ammoniumsalzen enthaltend ein Ammonium-Kation umfassend 6 bis 30 Kohlenstoff-Atome und (ii) organischem Sulfonat enthaltend wenigstens 7 Kohlenstoffatome, erfolgt. Dies entspricht einer bevorzugten Ausführungsform der Erfindung. In particular, it is preferred if the depolymerization of the polyurethane in step a) using a base with a pKb value at 25 ° C from 1 to 10, preferably 1 to 8, more preferably 1 to 7, in particular 1, 5 to 6, and a catalyst selected from the group consisting of (i) quaternary ammonium salts containing an ammonium cation containing from 6 to 30 carbon atoms and (ii) organic sulfonate containing at least 7 carbon atoms. This corresponds to a preferred embodiment of the invention.
Bevorzugte Basen umfassen ein Alkalimetallkation und/oder ein Ammoniumkation. Bevorzugte Basen sind hierbei Alkalimetallphosphate, Alkalimetallhydrogenphosphate, Alkalimetallcarbonate, Alkalimetallsilicate, Alkalimetallhydrogencarbonate, Alkalimetallacetate, Alkalimetallsulfite, Ammoniumhydroxide oder Mischungen vorgenannter. Bevorzugte Alkalimetalle sind dabei Na, K oder Li oder Mischungen vorgenannter, insbesondere Na oder K oder deren Mischungen; bevorzugtes Ammoniumkation ist NH4 +. Preferred bases include an alkali metal cation and/or an ammonium cation. Preferred bases here are alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal carbonates, alkali metal silicates, alkali metal hydrogen carbonates, alkali metal acetates, alkali metal sulfites, ammonium hydroxides or mixtures of the aforementioned. Preferred alkali metals are Na, K or Li or mixtures of the aforementioned, in particular Na or K or mixtures thereof; preferred ammonium cation is NH 4 + .
Besonders bevorzugte Basen sind K2CO3, Na2SiC>3, NH4OH, K3PO4, oder KOAc. Particularly preferred bases are K2CO3, Na2SiC>3, NH4OH, K3PO4, or KOAc.
Bevorzugt wird die Base als gesättigte alkalische Lösung in Wasser eingesetzt, wobei das Gewichtsverhältnis von gesättigter alkalischer Lösung zum PU im Bereich von vorzugsweise 0,5 bis 25, bevorzugt 0,5 bis 15, weiter bevorzugt 1 bis 10 insbesondere 2 bis 7 liegt. The base is preferably used as a saturated alkaline solution in water, the weight ratio of saturated alkaline solution to PU being in the range of preferably 0.5 to 25, preferably 0.5 to 15, more preferably 1 to 10, in particular 2 to 7.
Bevorzugte quartäre Ammoniumsalze haben die allgemeine Struktur: Ri R2 R3 R4 NX mit Ri, R2, R3 und R4 gleich oder unterschiedliche Kohlenwasserstoffgruppen gewählt von Alkyl, Aryl und/oder Arylalkyl, wobei Ri bis R4 vorzugsweise so gewählt sind, dass die Summe der Kohlenstoffatome des quartären Ammoniumkations 6 bis 14, vorzugsweise 7 bis 14, insbesondere 8 bis 13 beträgt. Preferred quaternary ammonium salts have the general structure: Ri R2 R3 R4 NX with Ri, R2, R3 and R4 identical or different hydrocarbon groups selected from alkyl, aryl and/or arylalkyl, where Ri to R4 are preferably selected such that the sum of the carbon atoms of the quaternary ammonium cation is 6-14, preferably 7-14, more preferably 8-13.
X ist gewählt aus Halogenid, vorzugsweise Chlorid und/oder Bromid, Hydrogensulfat, Alkylsulfat, vorzugsweise Methylsulfat oder Ethylsulfat, Carbonat, Hydrogencarbonat oder Carboxylat, vorzugsweise Acetat oder Hydroxid. X is selected from halide, preferably chloride and/or bromide, bisulfate, alkyl sulfate, preferably methyl sulfate or ethyl sulfate, carbonate, bicarbonate or carboxylate, preferably acetate or hydroxide.
Ganz besonders bevorzugte quartäre Ammoniumsalze sind Tributylmethylammoniumchlorid, Tetrabutylammouniumhydrogensulfat, Benzyltrimethylammoniumchlorid, Tributylmethylammoniumchlorid und/oder Trioctylmethylammoniummethylsulfat.
Das ebenfalls als Katalysator einsetzbare organische Sulfonat enthaltend wenigstens 7 Kohlenstoffatome umfasst vorzugsweise Alkylarylsulfonate, alpha-olefin Sulfonate, Petroleum- Sulfonate und/oder Naphthalen-Sulfonate. Very particularly preferred quaternary ammonium salts are tributylmethylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, tributylmethylammonium chloride and/or trioctylmethylammonium methyl sulfate. The organic sulfonate containing at least 7 carbon atoms which can also be used as a catalyst preferably includes alkylaryl sulfonates, alpha-olefin sulfonates, petroleum sulfonates and/or naphthalene sulfonates.
Bevorzugte Temperaturen für die Depolymerisation betragen 80 °C bis 200 °C, vorzugsweise 90 °C bis 180 °C, weiter bevorzugt 95 °C bis 170 °C und insbesondere 100 °C bis 160 °C. Preferred temperatures for the depolymerization are 80°C to 200°C, preferably 90°C to 180°C, more preferably 95°C to 170°C and in particular 100°C to 160°C.
Bevorzugte Reaktionszeiten für die Depolymerisation betragen 1 Minute bis 14 h, vorzugsweise 10 Minuten bis 12 h, bevorzugt 20 Minuten bis 11 h und insbesondere 30 Minuten bis 10 h. Preferred reaction times for the depolymerization are 1 minute to 14 hours, preferably 10 minutes to 12 hours, preferably 20 minutes to 11 hours and in particular 30 minutes to 10 hours.
Bevorzugt werden bei der Depolymerisation mindestens 0,5 Gew.-% Katalysator eingesetzt, bezogen auf das Gewicht des Polyurethans, vorzugsweise 0,5 bis 15 Gew.-%, weiter bevorzugt 1 bis 10 Gew.-%, noch weiter bevorzugt 1 bis 8 Gew.-%, wieder weiter bevorzugt 1 bis 7 Gew.-% und insbesondere 2 bis 6 Gew.-%. Preference is given to using at least 0.5% by weight of catalyst in the depolymerization, based on the weight of the polyurethane, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, even more preferably 1 to 8 % by weight, again more preferably 1 to 7% by weight and in particular 2 to 6% by weight.
Ein bevorzugtes Gewichtsverhältnis Base zu Polyurethan liegt im Bereich von 0,01 bis 50, vorzugsweise 0,1 bis 25, insbesondere 0,5 bis 20. A preferred weight ratio of base to polyurethane is in the range from 0.01 to 50, preferably from 0.1 to 25, in particular from 0.5 to 20.
Dies betraf die bevorzugte Variante 1 der Depolymerisation. This concerned the preferred variant 1 of the depolymerization.
Im Folgenden wird noch eine weitere besonders bevorzugte Variante, hier bevorzugte Variante 2 genannt, der Depolymerisation durch Hydrolyse beschrieben. Another particularly preferred variant, referred to here as preferred variant 2, of depolymerization by hydrolysis is described below.
Wenn die Depolymerisation des Polyurethans in Schritt a) unter Einsatz einer Base mit einem pKb Wert bei 25 °C von < 1 , vorzugsweise 0,5 bis -2, bevorzugt 0,25 bis -1 ,5 insbesondere 0 bis -1 , eines Katalysators aus der Gruppe der quartären Ammoniumsalze enthaltend ein Ammonium- Kation mit 6 bis 14 Kohlenstoff-Atomen, sofern das Ammonium-Kation keinen Benzylrest umfasst, oder aber enthaltend ein Ammonium-Kation mit 6 bis 12 Kohlenstoff-Atomen, sofern das Ammonium-Kation einen Benzylrest umfasst, erfolgt, so liegt eine weitere bevorzugte Ausführungsform der Erfindung vor. If the depolymerization of the polyurethane in step a) using a base with a pKb value at 25 ° C of <1, preferably 0.5 to -2, preferably 0.25 to -1, 5, in particular 0 to -1, a catalyst from the group of quaternary ammonium salts containing an ammonium cation with 6 to 14 carbon atoms if the ammonium cation does not contain a benzyl radical, or containing an ammonium cation with 6 to 12 carbon atoms if the ammonium cation contains a benzyl radical includes, takes place, there is a further preferred embodiment of the invention.
Bevorzugte Basen sind hierbei Alkalimetallhydroxide, Alkalimetalloxide, Erdalkalimetallhydroxide, Alkalimetalloxide oder deren Mischungen. Bevorzugte Alkalimetalle sind dabei Na, K oder Li oder Mischungen vorgenannter, insbesondere Na oder K oder deren Mischungen; bevorzugte Erdalkalimetalle sind Be, Mg, Ca, Sr oder Ba oder deren Mischungen, bevorzugt Mg oder Ca oder deren Mischungen. Eine ganz besonders bevorzugte Base ist NaOH. Preferred bases here are alkali metal hydroxides, alkali metal oxides, alkaline earth metal hydroxides, alkali metal oxides or mixtures thereof. Preferred alkali metals are Na, K or Li or mixtures of the aforementioned, in particular Na or K or mixtures thereof; preferred alkaline earth metals are Be, Mg, Ca, Sr or Ba or mixtures thereof, preferably Mg or Ca or mixtures thereof. A very particularly preferred base is NaOH.
Bevorzugte quartäre Ammoniumsalze haben die allgemeine Struktur: Ri R2 R3 R4 NX mit Ri, R2, R3 und R4 gleich oder unterschiedliche Kohlenwasserstoffgruppen gewählt von Alkyl, Aryl und Arylalkyl. Preferred quaternary ammonium salts have the general structure: Ri R 2 R 3 R 4 NX where Ri, R 2 , R 3 and R 4 are the same or different hydrocarbyl groups selected from alkyl, aryl and arylalkyl.
X ist gewählt aus Halogenid, vorzugsweise Chlorid und/oder Bromid, Hydrogensulfat, Alkylsulfat, vorzugsweise Methylsulfat oder Ethylsulfat, Carbonat, Hydrogencarbonat, Carboxylat, vorzugsweise Acetat oder Hydroxid.
Besonders bevorzugte quartäre Ammoniumsalze sind hierbei Benzyltrimethylammoniumchlorid oder Tributylmethylammoniumchlorid. X is selected from halide, preferably chloride and/or bromide, bisulfate, alkyl sulfate, preferably methyl sulfate or ethyl sulfate, carbonate, bicarbonate, carboxylate, preferably acetate or hydroxide. Particularly preferred quaternary ammonium salts here are benzyltrimethylammonium chloride or tributylmethylammonium chloride.
Bevorzugte Temperaturen für die Depolymerisation betragen 80 °C bis 200 °C, vorzugsweise 90 °C bis 180 °C, weiter bevorzugt 95 °C bis 170 °C und insbesondere 100 °C bis 160 °C. Bevorzugte Reaktionszeiten für die Depolymerisation betragen 1 Minute bis 14 h, vorzugsweise 10 Minuten bis 12 h, bevorzugt 20 Minuten bis 11 h und insbesondere 30 Minuten bis 10 h. Preferred temperatures for the depolymerization are 80°C to 200°C, preferably 90°C to 180°C, more preferably 95°C to 170°C and in particular 100°C to 160°C. Preferred reaction times for the depolymerization are 1 minute to 14 hours, preferably 10 minutes to 12 hours, preferably 20 minutes to 11 hours and in particular 30 minutes to 10 hours.
Bevorzugt werden bei der Depolymerisation zumindest 0,5 Gew.-% Katalysator eingesetzt, bezogen auf das Gewicht des Polyurethans, vorzugsweise 0,5 bis 15 Gew.-%, weiter bevorzugt 1 bis 10 Gew. - %, noch weiter bevorzugt 1 bis 8 Gew.-%, wieder weiter bevorzugt 1 bis 7 Gew.-% und insbesondere 2 bis 6 Gew.-%. Preference is given to using at least 0.5% by weight of catalyst in the depolymerization, based on the weight of the polyurethane, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, even more preferably 1 to 8 % by weight, again more preferably 1 to 7% by weight and in particular 2 to 6% by weight.
Ein bevorzugtes Gewichtsverhältnis Base zu Polyurethan liegt im Bereich von 0,01 bis 25, vorzugsweise 0,1 bis 15, bevorzugt 0,2 bis 10, insbesondere 0,5 bis 5. A preferred weight ratio of base to polyurethane is in the range from 0.01 to 25, preferably 0.1 to 15, preferably 0.2 to 10, in particular 0.5 to 5.
Bevorzugt wird eine alkalische Lösung eingesetzt, umfassend Base und Wasser, wobei die Konzentration der Base vorzugsweise größer 5 Gew.-% ist, vorzugsweise 5 bis 70 Gew.-%, bevorzugt 5 bis 60 Gew.-%, weiter bevorzugt 10 bis 50 Gew.-%, noch weiter bevorzugt 15 bis 40 Gew.-%, insbesondere 20 bis 40 Gew.-% beträgt, bezogen auf das Gewicht der alkalischen Lösung.An alkaline solution is preferably used, comprising base and water, the concentration of the base preferably being greater than 5% by weight, preferably 5 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight %, more preferably 15 to 40% by weight, especially 20 to 40% by weight, based on the weight of the alkaline solution.
Dies betraf die bevorzugte Variante 2 der Depolymerisation. This concerned the preferred variant 2 of the depolymerization.
Das in dem PU-Depolymerisationsprozess zu verwertende PU kann jedes PU-Produkt sein, insbesondere umfasst es einen Polyurethanschaum, vorzugsweise PU-Hartschaum, PU- Weichschaum, PU-Heißweichschaum, viskoelastischen PU-Schaum, HR-PU-Schaum, PU- Hypersoft-Schaum, halbharten PU-Schaum, thermoverformbarer PU-Schaum und/oder PU- Integralschaum. The PU to be used in the PU depolymerization process can be any PU product, in particular it comprises a polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam, viscoelastic PU foam, HR PU foam, PU hypersoft Foam, semi-rigid PU foam, thermoformable PU foam and/or integral PU foam.
Aus der beschriebenen Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators, der ausgewählt ist aus der Gruppe umfassend quartäre Ammoniumsalze enthaltend ein Ammonium Kation umfassend 6 bis 30 Kohlenstoff-Atome und organische Sulfonate enthaltend wenigstens 7 Kohlenstoffatome, bei Temperaturen vorzugsweise unter 200 °C können also Di- und/oder Polyamine erzeugt werden, welche, ggf. nach Abtrennung von anderen Depolymerisationsprodukten und für die Depolymerisation genutzten Reagenzien und ggf. vorherigen Reinigung, durch Phosgenierung zu Di- und/oder Polyisocyanaten umgewandelt werden. From the described depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst selected from the group comprising quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms, at temperatures preferably below 200° C di- and/or polyamines can thus be produced which, optionally after separating off other depolymerization products and reagents used for the depolymerization and optionally prior purification, are converted to di- and/or polyisocyanates by phosgenation.
Die Abtrennung und ggf. Reinigung der betreffenden Di- und/oder Polyamine kann wie folgt aus der über die Depolymerisierung erhaltenen Reaktionsmischung, die optional durch vorherige Filtration, Abtrennung der wässrigen Phase und/oder Abdestillation flüchtiger Komponenten vorbehandelt wurde, erfolgen: a) durch Destillation, bevorzugt Destillation unter vermindertem Druck im Bereich von 0,01 mbar bis 500 mbar, bevorzugt 0,05 mbar bis 350 mbar, weiter bevorzugt 0,1 mbar bis 200
mbar, besonders bevorzugt 0,5 mbar bis 100 mbar oder b) durch Extraktion mit gängigen organischen Lösungsmitteln wie z.B. Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Cyclohexan, Dichlormethan, Tetrahydrofuran, Heptan oder Octan. The di- and/or polyamines in question can be removed and, if necessary, purified as follows from the reaction mixture obtained via the depolymerization, which has optionally been pretreated by prior filtration, removal of the aqueous phase and/or distillation of volatile components: a) by distillation , preferably distillation under reduced pressure in the range from 0.01 mbar to 500 mbar, preferably 0.05 mbar to 350 mbar, more preferably 0.1 mbar to 200 mbar, particularly preferably 0.5 mbar to 100 mbar or b) by extraction with common organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, tetrahydrofuran, heptane or octane.
Bevorzugte, bei dem Prozess gewinnbare aromatische Di- und Polyamine umfassen Methylendiphenyldiamin (MDA, oder auch Diamine der Diphenylmethanreihe) als Isomere oder als Isomerengemisch, Polymethylenpolyphenylenpolyamin (PMDA, oder auch Polyamine der Diphenylmethanreihe), Gemische aus Methylendiphenyldiamin undPreferred, in the process recoverable aromatic di- and polyamines include methylenediphenyldiamine (MDA, or diamines of the diphenylmethane series) as isomers or as a mixture of isomers, polymethylenepolyphenylenepolyamine (PMDA, or polyamines of the diphenylmethane series), mixtures of methylenediphenyldiamine and
Polymethylenpolyphenylenpolyamin (MDA, oder auch Di- und Polyamine der Diphenylmethanreihe), Toluoldiamin (TDA) als reine Isomere oder Isomerengemisch der Isomere 2,4-Toluoldiamin und 2,6- Toluoldiamin, Isomere des Xylylendiamins (XDA), Isomere des Diaminobenzols, 2,6-Xylidin, 1 ,5- Naphthylendiamin (1 ,5-NDA), besonders bevorzugt sind Methylendiphenyldiamin (MDA, oder auch Diamine der Diphenylmethanreihe) als Isomerengemisch, Polymethylenpolyphenylenpolyamin (PMDA, oder auch Polyamine der Diphenylmethanreihe), Gemische aus Methylendiphenyldiamin und Polymethylenpolyphenylenpolyamin (MDA, oder auch Di- und Polyamine der Diphenylmethanreihe), Toluoldiamin (TDA) als reines Isomere oder Isomerengemisch der Isomere 2,4-Toluoldiamin und 2,6-Toluoldiamin, insbesondere bevorzugt ist Toluoldiamin (TDA) als reines Isomer oder Isomerengemisch der Isomere 2,4-Toluoldiamin und 2,6-Toluoldiamin. Polymethylenepolyphenylenepolyamine (MDA, or also di- and polyamines of the diphenylmethane series), toluenediamine (TDA) as pure isomers or isomer mixtures of the isomers 2,4-toluenediamine and 2,6-toluenediamine, isomers of xylylenediamine (XDA), isomers of diaminobenzene, 2, 6-xylidine, 1,5-naphthylenediamine (1,5-NDA), particular preference is given to methylenediphenyldiamine (MDA, or else diamines of the diphenylmethane series) as an isomer mixture, polymethylenepolyphenylenepolyamine (PMDA, or else polyamines of the diphenylmethane series), mixtures of methylenediphenyldiamine and polymethylenepolyphenylenepolyamine ( MDA, or also di- and polyamines of the diphenylmethane series), toluenediamine (TDA) as a pure isomer or isomer mixture of the isomers 2,4-toluenediamine and 2,6-toluenediamine, toluenediamine (TDA) as a pure isomer or isomer mixture of the isomers 2 is particularly preferred ,4-toluenediamine and 2,6-toluenediamine.
Bevorzugte, gewinnbare Di- und/oder Triamine auf Basis von aliphatischen oder cycloaliphatischen Kohlenwasserstoffen mit 2 bis 18 Kohlenstoffatomen, umfassen z. B. 1 ,4-Diaminobutan, 1 ,5- Diaminopentan, 1 ,6-Diaminohexan (HDA), 1 ,8-Diaminooctan, 1 ,9-Diaminononan, 1 ,10- Diaminodecan, 2,2-Dimethyl-l,5-diaminopentan, 2-Methyl-1 ,5-pentandiamin (MPDA), 2,4,4(oder - 2,2,4)-Trimethyl-1 ,6-diaminohexan (TMDA), 1 ,3- und 1 ,4-Diaminocyclohexan, 1-Amino-3,3,5- trimethyl-5-aminomethylcyclohexan (IPDA), 2,4-, oder 2,6-Diamino-1-methylcyclohexan (H6-TDA), 1-Amino-1-methyl-4(3)-aminomethylcyclohexan (AMCA), 1 ,3(und/oder 1 ,4)-Preferred recoverable di- and/or triamines based on aliphatic or cycloaliphatic hydrocarbons having 2 to 18 carbon atoms include, for. 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane (HDA), 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2,2-dimethyl-1,5 -diaminopentane, 2-methyl-1,5-pentanediamine (MPDA), 2,4,4(or - 2,2,4)-trimethyl-1,6-diaminohexane (TMDA), 1,3- and 1,4 -Diaminocyclohexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA), 2,4-, or 2,6-diamino-1-methylcyclohexane (H6-TDA), 1-amino-1-methyl -4(3)-aminomethylcyclohexane (AMCA), 1,3(and/or 1,4)-
Bis(aminomethyl)cyclohexan, Bis(aminomethyl)norbornan (NBDA), 4,4'(und/oder 2,4')- Diaminodicyclohexyl-methan, (cyclo)aliphatische Triamine mit bis zu 22 Kohlenstoffatomen, wie z.B. Triaminocyclohexan, Tris(aminomethyl)-cyclohexan, Triaminomethylcyclohexan, 1 ,8-Diamino-4- (aminomethyl)octan, 1 ,6,1-Undecantriamin, 1 ,7-Diamino-4-(3-aminopropyl)heptan, 1 ,6-Diamino-3- (aminomethyl)-hexan und/oder 1 ,3,5-Tris(aminomethyl)-cyclohexan. Bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane (NBDA), 4,4'(and/or 2,4')-diaminodicyclohexylmethane, (cyclo)aliphatic triamines having up to 22 carbon atoms, such as triaminocyclohexane, tris( aminomethyl)cyclohexane, triaminomethylcyclohexane, 1,8-diamino-4-(aminomethyl)octane, 1,6,1-undecanetriamine, 1,7-diamino-4-(3-aminopropyl)heptane, 1,6-diamino-3 - (aminomethyl)-hexane and/or 1,3,5-tris(aminomethyl)-cyclohexane.
Die Phosgenierung von Aminen zu Isocyanaten ist an sich bekannt. Sie kann vorzugsweise als Gasphasen-Phosgenierung der vorher in die Gasphase überführten Amine zusammen mit gasförmigem Phosgen bei Temperaturen von ca. 300 - 400 °C durchgeführt werden, wobei die Isocyanate im gasförmigen Zustand entstehen. Um die Entstehung ungewünschter Nebenreaktionen zwischen den entstehenden Isocyanaten und den als Ausgangsstoff verwendeten Aminen zu vermeiden, ist stets ein Phosgenüberschuss notwendig. Die Gasphasen-Phosgenierung erfolgt zumeist als kontinuierlicher Prozess. Die Entwicklung der adiabatischen Gasphasen-Phosgenierung, wie z.B. beschrieben in EP 1 616 857 AI, erlaubt es große Mengen Energie gegenüber herkömmlichen Phosgenierungsmethoden einzusparen. Neben der Gasphasen-Phosgenierung ist
die Verfahrensführung in derFlüssig-Phase möglich (Flüssigphasen-Phosgenierung), welche wegen der hohen Bedarfe an Lösungsmitteln jedoch Nachteile aufweist. The phosgenation of amines to form isocyanates is known per se. It can preferably be carried out as a gas-phase phosgenation of the amines previously converted into the gas phase together with gaseous phosgene at temperatures of about 300-400° C., the isocyanates being formed in the gaseous state. An excess of phosgene is always necessary to avoid the occurrence of undesirable side reactions between the isocyanates formed and the amines used as starting materials. Gas-phase phosgenation usually takes place as a continuous process. The development of adiabatic gas-phase phosgenation, as described, for example, in EP 1 616 857 A1, allows large amounts of energy to be saved compared with conventional phosgenation methods. In addition to the gas-phase phosgenation the process can be carried out in the liquid phase (liquid-phase phosgenation), which, however, has disadvantages due to the high solvent requirements.
Auf diese Weise ermöglicht die vorliegende Erfindung die Bereitstellung von aromatischen und/oder aliphatischen Di- und/oder Polyisocyanaten auf Basis von Polyurethan- Depolymerisationsprozessen, wie zuvor beschrieben. In this way, the present invention enables the provision of aromatic and/or aliphatic di- and/or polyisocyanates based on polyurethane depolymerization processes as described above.
Bevorzugte, durch das erfindungsgemäße Verfahren zugängliche recycelte aromatische Di- und Polyisocyanate sind Methylendiphenyldiisocyanat (MDI, oder auch Diisocyanate der Diphenylmethanreihe) als Isomere oder als Isomerengemisch, Polymethylenpolyphenylenpolyisocyanat (PMDI, oder auch Polyisocyanate derPreferred recycled aromatic di- and polyisocyanates accessible by the process according to the invention are methylenediphenyl diisocyanate (MDI, or also diisocyanates of the diphenylmethane series) as isomers or as a mixture of isomers, polymethylenepolyphenylene polyisocyanate (PMDI, or also polyisocyanates of
Diphenylmethanreihe), Gemische aus Methylendiphenyldiisocyanat undDiphenylmethane series), mixtures of methylenediphenyl diisocyanate and
Polymethylenpolyphenylenpolyisocyanat, Toluoldiisocyanat (TDI) als reine Isomere oder Gemisch der Isomere 2,4-Toluoldiisocanat (2,4-TDI) und 2,6-Toluoldiisocyanat (2,6-TDI), Isomere des Xylylendiisocyanats (XDI), Isomere des Diisocyanatobenzols, 2,6- Xylolisocyanat und/oder 1 ,5- Naphthylendiisocyanat (1 ,5-NDI), besonders bevorzugt sind Methylendiphenyldiisocyanat (MDI, oder auch Diisocyanate der Diphenylmethanreihe) als Isomere oder als Isomerengemisch,Polymethylene polyphenylene polyisocyanate, toluene diisocyanate (TDI) as pure isomers or a mixture of the isomers 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI), isomers of xylylene diisocyanate (XDI), isomers of diisocyanatobenzene, 2,6-xylene isocyanate and/or 1,5-naphthylene diisocyanate (1,5-NDI), particular preference being given to methylenediphenyl diisocyanate (MDI, or also diisocyanates of the diphenylmethane series) as isomers or as an isomer mixture,
Polymethylenpolyphenylenpolyisocyanat (PMDI, oder auch Polyisocyanate derPolymethylene polyphenylene polyisocyanate (PMDI, or polyisocyanates of
Diphenylmethanreihe), Gemische aus Methylendiphenyldiisocyanat und Polymethylenpolyphenylenpolyisocyanat und/oder Toluoldiisocyanat (TDI) als reine Isomere oderDiphenylmethane series), mixtures of methylenediphenyl diisocyanate and polymethylene polyphenylene polyisocyanate and/or toluene diisocyanate (TDI) as pure isomers or
Gemisch der Isomere 2,4-Toluoldiisocanat (2,4-TDI) und 2,6-Toluoldiisocyanat (2,6-TDI), insbesondere bevorzugt ist Toluoldiisocyanat (TDI) in isomerenreiner Form oder als Gemisch der Isomere 2,4-Toluoldiisocanat (2,4-TDI) und 2,6-Toluoldiisocyanat (2,6-TDI). Bevorzugte, durch das erfindungsgemäße Verfahren zugängliche recycelte aliphatische oder cycloaliphatische Di- oder Polyisocyanate enthalten 2 bis 18 Kohlenstoffatome und umfassen 1 ,4- Butandiisocyanat, 1 ,5-Pentandiisocyanat, 1 ,6-Hexandiisocyanat (HDI), 1 ,8-Octandiisocyanat, 1 ,9- Nonandiisocyanat, 1 ,10-Decandiisocyanat, 2,2-Dimethylpentan-1 ,5-diisocyanat, 2-Methyl-1 ,5- pentandiisocyanat (MPDI), 2,4,4(oder 2,2,4)-Trimethyl-1 ,6-hexandiisocyanat (TMDI), 1 ,3- und 1 ,4- Cyclohexandiisocyanat, 1-lsocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan (IPDI), 2,4-, oder 2,6-Diisocyanato-1-methylcyclohexan (H6-TDI), 1-lsocyanato-1-methyl-4(3)- isocyanatomethylcyclohexan (AMCI), 1 ,3(und/oder 1 ,4)-Bis(isocyanatomethyl)cyclohexan, Bis(isocyanatomethyl)norbornan (NBDI), 4,4'(und/oder 2,4')-Diisocyanatodicyclohexyl-methan, (cyclo)aliphatische Triisocyanate mit bis zu 22 Kohlenstoffatomen, wie z. B. Triisocyanatocyclohexan, Tris(isocyanatomethyl)-cyclohexan, Triisocyanato-methylcyclohexan, 1 ,8-Mixture of the isomers 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI), particular preference is given to toluene diisocyanate (TDI) in isomerically pure form or as a mixture of the isomers 2,4-toluene diisocyanate ( 2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI). Preferred recycled aliphatic or cycloaliphatic di- or polyisocyanates accessible by the process according to the invention contain 2 to 18 carbon atoms and include 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (HDI), 1,8-octane diisocyanate, 1 ,9-nonane diisocyanate, 1,10-decane diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, 2-methyl-1,5-pentane diisocyanate (MPDI), 2,4,4(or 2,2,4)- Trimethyl-1,6-hexane diisocyanate (TMDI), 1,3- and 1,4-cyclohexane diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- or 2,6-cyclohexane -Diisocyanato-1-methylcyclohexane (H6-TDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane (AMCI), 1,3(and/or 1,4)-bis(isocyanatomethyl)cyclohexane, bis( isocyanatomethyl)norbornane (NBDI), 4,4'(and/or 2,4')-diisocyanatodicyclohexylmethane, (cyclo)aliphatic triisocyanates having up to 22 carbon atoms, such as e.g. e.g. triisocyanatocyclohexane, tris(isocyanatomethyl)cyclohexane, triisocyanatomethylcyclohexane, 1,8-
Diisocyanato-4-(isocyanatomethyl)octan, 1 ,6,1- Undecantriisocyanat, 1 ,7-Diisocyanato-4-(3 - isocyanatopropyl)heptan, 1 ,6-Diisocyanato-3 -(isocyanatomethyl)-hexan und/oder 1 ,3,5- Tris(isocyanatomethy 1)-cyclohexan.
Die resultierenden Di- und/oder Polyisocyanate können wiederum verwendet werden, um daraus neue Polyurethane herzustellen. Diisocyanato-4-(isocyanatomethyl)octane, 1,6,1-undecane triisocyanate, 1,7-diisocyanato-4-(3-isocyanatopropyl)heptane, 1,6-diisocyanato-3-(isocyanatomethyl)hexane and/or 1, 3,5-tris(isocyanatomethyl 1)-cyclohexane. The resulting di- and/or polyisocyanates can in turn be used to produce new polyurethanes therefrom.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung eines Di- und/oder Polyisocyanates, erhalten nach einem erfindungsgemäßen Verfahren wie zuvor beschrieben, zur Herstellung von Polyurethan, insbesondere PU-Schaum. Solche Di- und/oder Polyisocyanate, die nach einem erfindungsgemäßen Verfahren wie zuvor beschrieben, erhalten wurden, werden im Sinne dieser Erfindung auch Recycling-Isocyanate genannt. A further object of the present invention is therefore the use of a di- and/or polyisocyanate, obtained by a process according to the invention as described above, for the production of polyurethane, in particular PU foam. Such di- and/or polyisocyanates which have been obtained by a process according to the invention as described above are also referred to as recycled isocyanates for the purposes of this invention.
Die Erfindung ermöglicht es, auch hohe Mengen an entsprechenden Recycling-Isocyanaten einzusetzen, wobei es zu keiner oder nur zu einer unwesentlichen Verminderung der Schaumqualität verglichen mit einem Schaum aus konventionell hergestelltem Isocyanaten, kommt. The invention also makes it possible to use large amounts of appropriate recycling isocyanates, with no or only an insignificant reduction in the foam quality compared with a foam made from conventionally produced isocyanates.
Es entspricht einer bevorzugten Ausführungsform der Erfindung, wenn bezogen auf die gesamte Isocanatkomponente mehr als 30 Gew,-%, vorzugsweise mehr als 50 Gew.-%, bevorzugt mehr als 70 Gew.-%, weiter bevorzugt mehr als 80 Gew.-%, insbesondere mehr als 95 Gew.-% Recycling- Isocyanat enthalten ist, erhalten nach einem erfindungsgemäßen Verfahren wie zuvor beschrieben.It corresponds to a preferred embodiment of the invention if, based on the total isocyanate component, more than 30% by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 95% by weight of recycled isocyanate is present, obtained by a process according to the invention as described above.
Entsprechend ist ein weiterer Gegenstand der Erfindung ein Verfahren zur Herstellung von Polyurethan, insbesondere PU-Schaumstoffen, durch Umsetzung Accordingly, a further object of the invention is a process for the production of polyurethane, in particular PU foams, by reaction
(a) mindestens einer Polyolkomponente mit (a) at least one polyol component
(b) mindestens einer Isocyanatkomponente in Gegenwart von (b) at least one isocyanate component in the presence of
(c) einem oder mehreren Katalysatoren, die die Reaktionen Isocyanat-Polyol und/oder Isocyanat-Wasser und/oder die Isocyanat-Trimerisierung katalysieren, (c) one or more catalysts which catalyze the isocyanate-polyol and/or isocyanate-water reactions and/or isocyanate trimerization,
(d) zumindest einem Schaumstabilisator sowie (d) at least one foam stabilizer and
(e) optional von ein oder mehreren chemischen oder physikalischen Treibmitteln, wobei die Isocyanatkomponente Recycling-Isocyanat umfasst, erhalten nach einem erfindungsgemäßen Verfahren wie zuvor beschrieben. (e) optionally one or more chemical or physical blowing agents, wherein the isocyanate component comprises recycled isocyanate obtained by a process according to the invention as described above.
Es entspricht einer bevorzugten Ausführungsform der Erfindung, wenn der Anteil an erfindungsgemäßem Recycling-Isocyanat bezogen auf die gesamte Isocanatkomponente mehr als 30 Gew,-%, vorzugsweise mehr als 50 Gew.-%, bevorzugt mehr als 70 Gew.-%, weiter bevorzugt mehr als 80 Gew.-%, insbesondere mehr als 95 Gew.-% beträgt. It corresponds to a preferred embodiment of the invention if the proportion of recycled isocyanate according to the invention, based on the total isocyanate component, is more than 30% by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 95% by weight.
Es entspricht einer weiteren bevorzugten Ausführungsform der Erfindung, wenn die Polyolkomponente ebenfalls Recycling-Polyol umfasst, insbesondere erhalten durch Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators, welcher aus der Gruppe bestehend aus quartären Ammoniumsalzen enthaltend ein
Ammonium Kation umfassend 6 bis 30 Kohlenstoff-Atome und organischen Sulfonaten enthaltend wenigstens 7 Kohlenstoffatome gewählt ist, wie zuvor beschrieben. It corresponds to a further preferred embodiment of the invention when the polyol component also comprises recycled polyol, obtained in particular by depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst which is selected from the group consisting of quaternary ammonium salts containing a ammonium cation comprising 6 to 30 carbon atoms and organic sulphonates containing at least 7 carbon atoms is selected as previously described.
Das erfindungsgemäße Verfahren unter Einsatz von Recycling-Isocyanat ermöglicht die Bereitstellung von allen bekannten PU-Schaumstoff Typen. In einer bevorzugten Ausführungsform der Erfindung ist der PU-Schaumstoff ein PU-Hartschaum, ein PU-Weichschaum, ein PU- Heißweichschaum (Standardschaum), ein viskoelastischer PU-Schaum, ein HR-PU-Schaum, ein PU-Hypersoft-Schaum, ein halbharter PU-Schaum, ein thermoverformbarer PU-Schaum oder ein PU-lntegralschaum, bevorzugt ein PU-Heißweichschaum, HR-PU-Schaum, PU-Hypersoft-Schaum oder viskoelastischer PU-Schaum. PU-Heißweichschaum ist am meisten bevorzugt. Gemäß einer bevorzugten Ausführungsform der Erfindung, insbesondere zur Herstellung von Formschäumen und hochelastischen PU-Weichschäumen, werden als I so cyanatkom ponente bevorzugt Toluoldiisocyanat (TDI) als Isomerengemisch aus 2,4- und 2,6- Toluoldiisocyanat und/oder Methylendiphenyldiisocyanat (MDI) als Isomerengemisch aus 4,4‘-, 2,4‘- und 2,2‘- Methylendiphenyldiisocyanat und/oder Polyphenylpolymethylenpolyisocyanate (Roh-MDI oder polymeres MDI) eingesetzt. The method according to the invention using recycled isocyanate makes it possible to provide all known types of PU foam. In a preferred embodiment of the invention, the PU foam is a PU rigid foam, a PU flexible foam, a PU hot flexible foam (standard foam), a viscoelastic PU foam, an HR PU foam, a PU hypersoft foam semi-rigid PU foam, a thermoformable PU foam or a PU integral foam, preferably a PU hot flexible foam, HR PU foam, PU hypersoft foam or viscoelastic PU foam. PU hot flexible foam is most preferred. According to a preferred embodiment of the invention, in particular for the production of molded foams and highly elastic flexible PU foams, toluene diisocyanate (TDI) as an isomer mixture of 2,4- and 2,6-toluene diisocyanate and/or methylene diphenyl diisocyanate (MDI) is used as the isocyanate component Isomer mixture of 4,4'-, 2,4'- and 2,2'-methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI) are used.
Besonders bevorzugt wird TDI in einem Isomerenverhältnis von 80 zu 20 (2,4-TDI zu 2,6-TDI) und/oder Methylendiphenyldiisocyanat (MDI) als Isomerengemisch aus 4,4‘-, 2,4‘- und 2,2‘- Methylendiphenyldiisocyanat und/oder Polyphenylpolymethylenpolyisocyanate (Roh-MDI oder polymeres MDI) eingesetzt. In einer weiteren bevorzugten Ausführungsform der Erfindung, der Herstellung von Heißweichschäumen (Standardschäumen) betreffend, wird als Isocyanatkomponente bevorzugt Toluoldiisocyanat (TDI) als Isomerengemisch aus 2,4- und 2,6-Toluoldiisocyanat eingesetzt. Besonders bevorzugt wird TDI in einem Isomerenverhältnis von 80 zu 20 (2,4-TDI zu 2,6-TDI) eingesetzt. Eine weitere bevorzugte Ausführungsform der Erfindung stellt die Herstellung viskoelatischer Schäume (auch Visko-Schäume) dar. Für viskoelastische Polyurethanschäume werden als Isocyanatkomponente bevorzugt Toluoldiisocyanat (TDI) als Isomerengemisch aus 2,4- und 2,6- Toluoldiisocyanat und/oder Methylendiphenyldiisocyanat (MDI) als Isomerengemisch aus 4,4‘-, 2,4‘- und 2,2‘-Methylendiphenyldiisocyanat und/oder Polyphenylpolymethylenpolyisocyanate (Roh-MDI oder polymeres MDI) eingesetzt. Besonders bevorzugt wird TDI in einem Isomerenverhältnis von 80 zu 20 (2,4-TDI zu 2,6-TDI) und/oder in einem Isomerenverhältnis von 65 zu 35 (2,4-TDI zu 2,6-TDI) und/oder Methylendiphenyldiisocyanat als Gemisch aus 4,4‘, 2,4‘- und 2,2‘-Particular preference is given to TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and/or methylenediphenyl diisocyanate (MDI) as an isomer mixture of 4,4'-, 2,4'- and 2,2'- - Methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI) used. In a further preferred embodiment of the invention, relating to the production of hot flexible foams (standard foams), toluene diisocyanate (TDI) as an isomer mixture of 2,4- and 2,6-toluene diisocyanate is preferably used as the isocyanate component. TDI is particularly preferably used in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI). Another preferred embodiment of the invention is the production of viscoelastic foams (also viscous foams). used as an isomer mixture of 4,4'-, 2,4'- and 2,2'-methylenediphenyl diisocyanate and/or polyphenylpolymethylene polyisocyanates (crude MDI or polymeric MDI). TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and/or in an isomer ratio of 65 to 35 (2,4-TDI to 2,6-TDI) and/or is particularly preferred Methylenediphenyl diisocyanate as a mixture of 4,4', 2,4'- and 2,2'-
Methylendiphenyldiisocyanaten und Polyphenylpolymethylenpolyisocyanat eingesetzt. Die genannten aromatischen Polyisocyanate können einzeln oder auch in Form ihrer Mischungen eingesetzt werden. Bevorzugt werden zur Herstellung viskoelastischer Polyurethanschäume Mischungen aus TDI in einem Isomerenverhältnis von 80 zu 20 (2,4-TDI zu 2,6-TDI) und TDI in einem Isomerenverhältnis von 65 zu 35 (2,4-TDI zu 2,6-TDI) eingesetzt oder Mischungen aus TDI in einem Isomerenverhältnis von 80 zu 20 (2,4-TDI zu 2,6-TDI) und Methylendiphenyldiisocyanat als
Gemisch aus 4,4‘, 2,4‘- und 2,2‘-Methylendiphenyldiisocyanaten undMethylenediphenyl diisocyanates and polyphenylpolymethylene polyisocyanate used. The aromatic polyisocyanates mentioned can be used individually or else in the form of their mixtures. Mixtures of TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and TDI in an isomer ratio of 65 to 35 (2,4-TDI to 2,6-TDI) are preferred for the production of viscoelastic polyurethane foams ) used or mixtures of TDI in an isomer ratio of 80 to 20 (2,4-TDI to 2,6-TDI) and methylenediphenyl diisocyanate as Mixture of 4,4', 2,4'- and 2,2'-methylenediphenyl diisocyanates and
Polyphenylpolymethylenpolyisocyanat eingesetzt. Polyphenylpolymethylene polyisocyanate used.
Die Herstellung der PU-Schäume kann grundsätzlich auf die übliche Weise und wie im Stand der Technik beschrieben erfolgen. Sie ist dem Fachmann wohlbekannt. Eine grundsätzliche Übersicht findet sich z. B. in G. Oertel, Polyurethane Handbook, 2nd Edition, Hanser/GardnerPublications Inc. , Cincinnati, Ohio, 1994, S. 177-247. Weitere Angaben zu den einsetzbaren Ausgangsstoffen, Katalysatoren sowie Hilfs- und Zusatzstoffen finden sich beispielsweise im Kunststoffhandbuch, Band 7, Polyurethane, Carl-Hanser- Verlag München, 1. Auflage 1966, 2. Auflage, 1983 und 3. Auflage, 1993. Wenn die Herstellung der erfindungsgemäßen PU-Schäume unter Einsatz von f) Wasser, g) einem oder mehreren organischen Lösungsmitteln, h) einem oder mehreren Stabilisatoren gegen oxidativen Abbau, insbesondere Antioxidantien, i) einem oder mehreren Flammschutzmitteln, und/oder j) einem oder mehreren weiteren Zusatzstoffen, vorzugsweise ausgewählt aus der Gruppe der Tenside, Biozide, Farbstoffe, Pigmente, Füllstoffe, Antistatik-Additive, Vernetzer,In principle, the PU foams can be produced in the usual manner and as described in the prior art. It is well known to those skilled in the art. A basic overview can be found e.g. B. in G. Oertel, Polyurethane Handbook, 2nd Edition, Hanser/Gardner Publications Inc., Cincinnati, Ohio, 1994, pp. 177-247. Further information on the usable starting materials, catalysts and auxiliaries and additives can be found, for example, in the Plastics Handbook, Volume 7, Polyurethane, Carl Hanser Verlag Munich, 1st edition 1966, 2nd edition, 1983 and 3rd edition, 1993. If the Production of the PU foams according to the invention using f) water, g) one or more organic solvents, h) one or more stabilizers against oxidative degradation, in particular antioxidants, i) one or more flame retardants, and/or j) one or more others Additives, preferably selected from the group of surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers,
Kettenverlängerer, Zellöffner, Duftstoffe, Zellvergröberer, Weichmacher, Härtevermittler, Aldehydfänger, Additive für Beständigkeit von PU-Schäumen gegenüber Hydrolyse, Kompatibilisatoren (Emulgatoren), Adhäsionsvermittler, Hydrophobierungs-Additive, Flammlaminierungs-Additive, Additive für die Verhinderung von Cold Flow, Druckverformungsrest vermindernde Additive, Additive zur Einstellung der Glasübergangstemperatur, temperaturkontrollierende Additive und/oder Geruchsverminderer erfolgt, so liegt eine weitere bevorzugte Ausführungsform der Erfindung vor. Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Zusammensetzung, geeignet zur Herstellung von Polyurethan-Schaum, umfassend mindestens eine Polyolkomponente, mindestens eine Isocyanatkomponente, Katalysator, Schaumstabilisator, Treibmittel, optional Hilfsmittel, wobei die Isocyanatkomponente Recycling-Isocyanat umfasst, wie zuvor beschrieben. Chain extenders, cell openers, fragrances, cell coarseners, plasticizers, hardeners, aldehyde scavengers, additives for resistance of PU foams to hydrolysis, compatibilizers (emulsifiers), adhesion promoters, hydrophobing additives, flame lamination additives, additives for preventing cold flow, additives to reduce compression set , additives for adjusting the glass transition temperature, temperature-controlling additives and/or odor reducers, a further preferred embodiment of the invention is present. Another subject of the present invention is a composition suitable for the production of polyurethane foam, comprising at least one polyol component, at least one isocyanate component, catalyst, foam stabilizer, blowing agent, optional auxiliaries, the isocyanate component comprising recycled isocyanate, as described above.
Bevorzugte optionale Hilfsmittel umfassen Tenside, Biozide, Farbstoffe, Pigmente, Füllstoffe, Antistatik-Additive, Vernetzer, Kettenverlängerer, Zellöffner wie z.B. beschrieben in EP 2998333A1 , Duftstoffe, Zellvergröberer wie z.B. beschrieben in EP 2986661 B1 , Weichmacher, Härtevermittler, Additive für die Verhinderung von Cold Flow wie z.B. beschrieben in DE 2507161C3, WO 2017029054A1 , Aldehydfänger wie z.B. beschrieben in WO 2021/013607A1 , Additive für Beständigkeit von PU-Schäumen gegenüber Hydrolyse wie z.B. beschrieben in US 2015/0148438A1 , Kompatibilisatoren (Emulgatoren), Adhäsionsvermittler, Hydrophobierungs-Preferred optional auxiliaries include surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers such as described in EP 2998333A1, fragrances, cell coarsening agents such as described in EP 2986661 B1, plasticizers, hardeners, additives for the prevention of Cold flow as described, for example, in DE 2507161C3, WO 2017029054A1, aldehyde scavengers as described, for example, in WO 2021/013607A1, additives for resistance of PU foams to hydrolysis, as described, for example, in US 2015/0148438A1, compatibilizers (emulsifiers), adhesion promoters, hydrophobing
Additive, Flammlaminierungs-Additive wie z.B. beschrieben in EP 2292677A1 ,
Druckverformungsrest vermindernde Additive, Additive zur Einstellung der Glasübergangstemperatur, temperaturkontrollierende Additive und/oder Geruchsverminderer.Additives, flame lamination additives such as described in EP 2292677A1, Compression set reducing additives, glass transition temperature adjusting additives, temperature controlling additives and/or odor reducing agents.
Die erfindungsgemäß eingesetzten Verbindungen, deren Herstellung, die Verwendung der Verbindungen zur Herstellung der PU-Schäume sowie die PU-Schäume selbst werden nachfolgend noch weiter beispielhaft beschrieben, ohne dass die Erfindung auf diese beispielhaften Ausführungsformen beschränkt sein soll. Sind nachfolgend Bereiche, allgemeine Formeln oder Verbindungsklassen angegeben, so sollen diese nicht nur die entsprechenden Bereiche oder Gruppen von Verbindungen umfassen, die explizit erwähnt sind, sondern auch alle Teilbereiche und Teilgruppen von Verbindungen, die durch Herausnahme von einzelnen Werten (Bereichen) oder Verbindungen erhalten werden können. Werden im Rahmen der vorliegenden Beschreibung Dokumente zitiert, so soll deren Inhalt, insbesondere bezüglich der in Bezug genommenen Sachverhalte vollständig zum Offenbarungsgehalt der vorliegenden Erfindung gehören. Werden nachfolgend Angaben in Prozent gemacht, so handelt es sich, wenn nicht anders angegeben um Angaben in Gewichts-%. Werden nachfolgend Mittelwerte angegeben, so handelt es sich, wenn nicht anders angegeben um das Zahlenmittel. Werden nachfolgend Stoffeigenschaften, wie z. B. Viskositäten oder ähnliches angegeben, so handelt es sich, wenn nicht anders angegeben, um die Stoffeigenschaften bei 25 °C. Werden in der vorliegenden Erfindung chemische (Summen-) Formeln verwendet, so können die angegebenen Indizes sowohl absolute Zahlen als auch Mittelwerte darstellen. Bei polymeren Verbindungen stellen die Indizes vorzugsweise Mittelwerte dar. Das erfindungsgemäße Verfahren ermöglicht den Zugang zu allen PU-Schaumstoffen. Bevorzugte PU-Schaumstoffe im Sinne dieser Erfindung sind PU-Weichschaumstoffe und PU-Hartschaumstoffe. PU-Weichschaumstoffe und PU-Hartschaumstoffe sind feststehende technische Begriffe. Der bekannte und prinzipielle Unterschied zwischen Weichschaumstoffen und Hartschaumstoffen ist, dass ein Weichschaumstoff ein elastisches Verhalten zeigt und damit die Verformung reversibel ist. Der Hartschaumstoff wird demgegenüber dauerhaft verformt. Im Folgenden werden verschiedene, im Rahmen der Erfindung bevorzugte Untergruppen von Schaumstoffen genauer beschrieben, wobei im Rahmen dieser Erfindung einfachheitshalber der Begriff des „Schaums“ synonym für den des „Schaumstoffs“ verwendet wird. The compounds used according to the invention, their production, the use of the compounds for the production of the PU foams and the PU foams themselves are described in more detail below by way of example, without the invention being restricted to these exemplary embodiments. If ranges, general formulas or compound classes are specified below, these should not only include the corresponding ranges or groups of compounds that are explicitly mentioned, but also all sub-ranges and sub-groups of compounds that are obtained by removing individual values (ranges) or compounds can become. If documents are cited in the context of the present description, then their content, in particular with regard to the facts referred to, should fully belong to the disclosure content of the present invention. If percentages are given below, unless otherwise stated, these are percentages by weight. If mean values are given below, they are the numerical mean unless otherwise stated. If the following material properties, such. For example, if viscosities or the like are given, these are the material properties at 25 °C unless otherwise stated. If chemical (sum) formulas are used in the present invention, the indices given can represent both absolute numbers and mean values. In the case of polymeric compounds, the indices preferably represent mean values. The process according to the invention enables access to all PU foams. Preferred PU foams for the purposes of this invention are flexible PU foams and rigid PU foams. PU flexible foams and PU rigid foams are established technical terms. The well-known and fundamental difference between flexible foams and rigid foams is that flexible foam shows elastic behavior and the deformation is therefore reversible. The hard foam, on the other hand, is permanently deformed. Various subgroups of foams that are preferred within the scope of the invention are described in more detail below, with the term “foam” being used synonymously for “foam” within the scope of this invention for the sake of simplicity.
Im Rahmen der vorliegenden Erfindung wird unter Polyurethan-Hartschaum insbesondere ein Schaumstoff gemäß DIN 7726:1982-05 verstanden, der eine Druckfestigkeit nach DIN 53421 :1984- 06 von vorteilhafterweise > 20 kPa, vorzugsweise > 80 kPa, bevorzugt > 100 kPa, weiter bevorzugt >150 kPa, besonders bevorzugt >180 kPa aufweist. Weiterhin verfügt der Polyurethan-Hartschaum nach DIN EN ISO 4590:2016-12 vorteilhafterweise über eine Geschlossenzelligkeit von größer 50%, vorzugsweise größer 80% und besonders bevorzugt größer 90%. PU-Hartschäume werden meist für Isolationszwecke eingesetzt. In the context of the present invention, rigid polyurethane foam is understood in particular as meaning a foam according to DIN 7726:1982-05, which more preferably has a compressive strength according to DIN 53421:1984-06 of advantageously >20 kPa, preferably >80 kPa, preferably >100 kPa >150 kPa, particularly preferably >180 kPa. Furthermore, according to DIN EN ISO 4590:2016-12, the rigid polyurethane foam advantageously has a closed cell content of more than 50%, preferably more than 80% and particularly preferably more than 90%. PU rigid foams are mostly used for insulation purposes.
PU-Weichschäume sind elastisch und verformbar und meistens offenzeilig. Dadurch kann die Luft bei Kompression leicht entweichen. Der Oberbegriff des PU-Weichschaums schließt dabei insbesondere folgende der Fachperson bekannte Schaumtypen, namentlich PU-Heißweichschaum
(Standardschaum), PU-Kaltschaum (auch hochelastische oder High Resilience-Schaum), Hypersoft PU-Schaum, viskoelastischen PU-Weichschaum und PU-Esterschäume (aus Polyester-Polyolen) ein. Im Folgenden seien die verschiedenen PU-Weichschaumtypen noch einmal näher erläutert bzw. voneinander abgegrenzt. Der entscheidende Unterschied zwischen einem PU-Heißweichschaum und einem PU- Kaltweichschaum besteht in den unterschiedlichen mechanischen Eigenschaften. Die Differenzierung zwischen PU-Heißweichschäumen und PU-Kaltweichschäumen kann insbesondere durch die Rückprallelastizität, auch „Ball Rebound“ (BR) oder „Resilience“ genannt, erfolgen. Ein Verfahren zur Bestimmung der Rückprallelastizität ist beispielsweise in der DIN EN ISO 8307:2008- 03 beschrieben. Hierbei wird eine Stahlkugel mit festgelegter Masse aus einer bestimmten Höhe auf den Probenkörper fallen gelassen und dann die Höhe des Rückpralls in % der Abwurfhöhe gemessen. PU-Heißweichschäume weisen Rückprall-Werte von vorzugsweise 1 % bis maximal 50 % auf. Die Höhe des Rückpralls liegt im Falle von PU-Kaltweichschäumen vorzugsweise im Bereich > 50%. Die hohe Rückprallelastizität von PU-Kaltweichschäumen resultiert aus einer verhältnismäßig unregelmäßigen Zellgrößenverteilung. Ein weiteres mechanisches Kriterium stellt der SAG- oder Komfortfaktor dar. Hierbei wird eine Schaumstoffprobe gemäß DIN EN ISO 2439:2009-05 komprimiert und das Verhältnis der Druckspannung bei 65% und 25% Kompression gemessen. PU-Heißweichschäume haben einen Komfortfaktor von vorzugsweise < 2,5. Bei PU- Kaltweichschäumen liegt der Komfortfaktor vorzugsweise bei > 2,5. Bei der Herstellung von PU- Kaltweichschäumen werden insbesondere gegenüber Isocyanaten besonders reaktive Polyether- Polyole mit einem hohen Anteil primärer Hydroxylgruppen und zahlenmittleren Molmassen > 4000 g/mol eingesetzt. Dagegen werden bei PU-Heißweichschäumen gewöhnlich überwiegend reaktionsträgere Polyole mit sekundären OH-Gruppen und einer mittleren Molmasse < 4000 g/mol verwendet. Neben Kaltblockschäumen stellen Kaltformschäume, die z.B. in Automobil-Sitzpolstern genutzt werden, eine Kernanwendung von PU-Kaltschäumen dar. PU flexible foams are elastic and deformable and mostly open-celled. This allows the air to escape easily when compressed. The generic term of flexible PU foam includes in particular the following types of foam known to those skilled in the art, namely hot flexible PU foam (standard foam), PU cold foam (also highly elastic or high resilience foam), Hypersoft PU foam, viscoelastic PU soft foam and PU ester foams (made of polyester polyols). The different types of flexible PU foam are explained in more detail below and differentiated from one another. The crucial difference between a PU hot flexible foam and a PU cold flexible foam is the different mechanical properties. The differentiation between PU hot flexible foams and PU cold flexible foams can be made in particular by the rebound elasticity, also known as "ball rebound" (BR) or "resilience". A method for determining the rebound resilience is described, for example, in DIN EN ISO 8307:2008-03. A steel ball with a specified mass is dropped onto the specimen from a certain height and the height of the rebound is then measured as a percentage of the dropping height. PU hot flexible foams have rebound values of preferably 1% to a maximum of 50%. In the case of PU cold flexible foams, the level of rebound is preferably in the range >50%. The high rebound resilience of PU cold flexible foams results from a relatively irregular cell size distribution. Another mechanical criterion is the SAG or comfort factor. Here, a foam sample is compressed in accordance with DIN EN ISO 2439:2009-05 and the ratio of the compressive stress at 65% and 25% compression is measured. PU hot flexible foams have a comfort factor of preferably < 2.5. In the case of PU cold flexible foams, the comfort factor is preferably > 2.5. In the production of PU cold flexible foams, polyether polyols which are particularly reactive towards isocyanates and have a high proportion of primary hydroxyl groups and number-average molar masses >4000 g/mol are used. On the other hand, in the case of PU hot flexible foams, predominantly inert polyols with secondary OH groups and an average molar mass of <4000 g/mol are usually used. In addition to cold block foams, cold molded foams, which are used in automotive seat cushions, for example, represent a core application of PU cold foams.
Ebenfalls erfindungsgemäß bevorzugt sind Hypersoft-PU-Schäume, die eine Subkategorie der PU- Weichschäume darstellen. Hypersoft-PU-Schäume haben Druckspannungen bestimmt nach DIN EN ISO 3386-1 : 1997 + A1 :2010von vorzugsweise < 2,0 kPa und weisen Eindruckhärten bestimmt nach DIN EN ISO 2439:2009-05 von vorzugsweise < 80 N auf. Hypersoft PU-Schäume können durch unterschiedliche bekannte Verfahren hergestellt werden: Durch Verwendung eines sogenannten Hypersoft-Polyols in Kombination mit sogenannten Standard-Polyolen und/oder durch ein spezielles Herstellverfahren bei dem Kohlendioxid während des Schäumprozesses zudosiert wird. Bedingt durch eine ausgeprägte Offenzelligkeit haben Hypersoft-PU-Schäume eine hohe Luftdurchlässigkeit, begünstigen den Feuchtigkeitstransport in Anwendungsprodukten und tragen zur Vermeidung von Wärmestau bei. Die zur Herstellung von Hypersoft PU-Schäumen eingesetzten Hypersoft-Polyole zeichnen sich insbesondere durch einen sehr hohen Anteil primärer OH-Gruppen von mehr als 60% aus. Also preferred according to the invention are hypersoft PU foams, which represent a subcategory of flexible PU foams. Hypersoft PU foams have compressive stresses determined according to DIN EN ISO 3386-1:1997 + A1:2010 of preferably <2.0 kPa and have indentation hardnesses determined according to DIN EN ISO 2439:2009-05 of preferably <80 N. Hypersoft PU foams can be manufactured using a variety of known methods: by using a so-called hypersoft polyol in combination with so-called standard polyols and/or by using a special manufacturing method in which carbon dioxide is added during the foaming process. Due to a pronounced open cell structure, Hypersoft PU foams have a high level of air permeability, promote the transport of moisture in application products and help to prevent heat build-up. The Hypersoft polyols used to produce Hypersoft PU foams are characterized in particular by a very high proportion of primary OH groups of more than 60%.
Eine spezielle Klasse der PU-Weichschäume ist die der viskoelastischen PU-Schäume (PU-Visko- schäume), welche ebenfalls erfindungsgemäß bevorzugt sind. Diese sind auch unter dem Namen
Memory Foam (zu Deutsch etwa "Schaum mit Erinnerungsvermögen") bekannt und zeichnen sich sowohl durch eine geringe Rückprallelastizität nach DIN EN ISO 8307:2008-03 von vorzugsweise < 15% als auch durch eine langsame, graduelle Rückverformung nach einer erfolgten Kompression aus (Rückverformungszeit vorzugsweise 2 - 13 s). Im Gegensatz zu PU-Heißweichschäumen und PU-Kaltweichschäumen, die eine Glasübergangstemperatur von kleiner -32 °C aufweisen, ist für viskoelastische PU-Schäume die Glasübergangstemperatur vorzugsweise in einen Bereich von -20 bis +15 °C verschoben. Von solcher „Struktur- Viskoelastizität" bei offenzeiligen viskoelastischen PU- Weichschäumen, die im Wesentlichen auf der Glastemperatur des Polymers beruht (auch chemische Viskoschäume genannt), ist ein pneumatischer Effekt zu unterscheiden. In letzterem Falle handelt es sich um eine relativ geschlossene Zellstruktur (geringe Porosität). Durch die geringe Luftdurchlässigkeit strömt die Luft nach einer Kompression nur langsam wieder ein, was eine verlangsamte Rückverformung zur Folge hat (auch pneumatische Viskoschäume genannt). In vielen Fällen sind beide Effekte in einem Viskoschaum kombiniert. PU-Viskoschäume werden wegen ihrer energie- und schallabsorbierenden Eigenschaften sehr geschätzt. A special class of flexible PU foams is that of viscoelastic PU foams (PU viscose foams), which are also preferred according to the invention. These are also under the name Memory foam is known and is characterized both by a low rebound elasticity according to DIN EN ISO 8307:2008-03 of preferably <15% and by a slow, gradual recovery after compression (recovery time preferably 2 - 13 s). In contrast to hot flexible PU foams and cold flexible PU foams, which have a glass transition temperature of less than -32°C, the glass transition temperature for viscoelastic PU foams is preferably shifted to a range from -20 to +15°C. A pneumatic effect must be distinguished from such "structural viscoelasticity" in open-cell viscoelastic PU foams, which is essentially based on the glass transition temperature of the polymer (also known as chemical viscofoams). In the latter case, there is a relatively closed cell structure (low porosity). Due to the low air permeability, the air only flows back in slowly after compression, which results in a slower recovery (also called pneumatic visco-foams). In many cases, both effects are combined in one visco-foam. PU visco-foams are used because of their energy - and sound-absorbing properties.
Eine besonders für Anwendungen im Automobilbereich wichtige Klasse an PU-Schäumen, die sich in Bezug auf die Eigenschaften zwischen denen von Hart- und Weichschaumstoffen einordnen lässt, besteht aus den halbharten (semiflexiblen) PU-Schäumen. Auch diese sind erfindungsgemäß bevorzugt. Wie die meisten PU-Schaumsysteme nutzen semiflexible Schaumsysteme auch die Isocyanat/Wasser-Reaktion und das dabei entstehende CO2 als Treibmittel der Schaumbildung. Die Rückprallelastizität ist in der Regel geringer als von klassischen Weichschäumen, insbesondere von Kaltschäumen. Semiflexible Schäume weisen eine höhere Härte als konventionelle Weichschäume auf. Ein charakteristisches Merkmal von semiflexiblen Schäumen ist deren hohe Offenzelligkeit (vorzugsweise > 90% der Zellen). Die Dichten von semiflexiblen Schäumen können deutlich über denen von Weich- und Hartschäumen liegen. A class of PU foams that is particularly important for applications in the automotive sector and that can be classified between those of rigid and flexible foams in terms of properties consists of semi-rigid (semi-flexible) PU foams. These are also preferred according to the invention. Like most PU foam systems, semi-flexible foam systems also use the isocyanate/water reaction and the resulting CO2 as a foaming agent. The rebound resilience is generally lower than that of classic flexible foams, especially cold foams. Semi-flexible foams are harder than conventional flexible foams. A characteristic feature of semi-flexible foams is their high number of open cells (preferably >90% of the cells). The densities of semi-flexible foams can be significantly higher than those of flexible and rigid foams.
Als Polyolkomponenten werden vorzugsweise ein oder mehrere Polyole eingesetzt, welche zwei oder mehr OH-Gruppen aufweisen. Bevorzugte einsetzbare Polyole sind alle zur Herstellung von Polyurethansystemen, insbesondere Polyurethanschaumstoffen üblicherweise verwendeten Polyether-Polyole und Polyester-Polyole. One or more polyols which have two or more OH groups are preferably used as polyol components. Preferred polyols which can be used are all the polyether polyols and polyester polyols customarily used for the production of polyurethane systems, in particular polyurethane foams.
Polyether-Polyole können z. B. durch Umsetzung von mehrwertigen Alkoholen oder Aminen mit Alkylenoxiden gewonnen werden. Polyester-Polyole basieren vorzugsweise auf Estern mehrwertiger Carbonsäuren mit mehrwertigen Alkoholen (meist Glycolen). Die mehrwertigen Carbonsäuren können entweder aliphatisch (beispielsweise Adipinsäure), oder aromatisch (beispielsweise Phthalsäure oder Terephthalsäure) sein. Polyether polyols can, for. B. be obtained by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are preferably based on esters of polybasic carboxylic acids with polyhydric alcohols (mostly glycols). The polybasic carboxylic acids can be either aliphatic (e.g. adipic acid) or aromatic (e.g. phthalic acid or terephthalic acid).
Eine wichtige Klasse optional einsetzbarer Polyole, die aus natürlichen Ölen, wie z.B. Palm- oder Sojaöl zugänglich ist, sogenannte „Natural oil based polyols“ (NOPs) kann auf Basis von nachwachsenden Rohstoffen gewonnen werden. NOPs sind für eine nachhaltigere Herstellung von PU-Schäumen mit Blick auf die langfristig begrenzte Verfügbarkeit fossiler Ressourcen, namentlich Öl, Kohle und Gas, und vor dem Hintergrund steigender Rohölpreise von zunehmendem Interesse
und bereits vielfach bei der Herstellung von Polyurethanschäumen beschrieben (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091 , WO 2006/116456 und EP 1678232). Mittlerweile sind auf dem Markt eine Reihe dieser Polyole von verschiedenen Herstellern verfügbar (WO 2004/020497, US 2006/0229375, WO 2009/058367). In Abhängigkeit vom Basis-Rohstoff (z.B. Sojabohnenöl, Palmöl oder Rizinusöl) und die daran angeschlossene Aufarbeitung ergeben sich Polyole mit unterschiedlichem Eigenschaftsbild. Hierbei können im Wesentlichen zwei Gruppen unterschieden werden: a) Polyole auf Basis nachwachsender Rohstoffe, die soweit modifiziert werden, dass sie zu 100 % zur Herstellung von Polyurethanen eingesetzt werden können (W02004/020497, US2006/0229375); b) Polyole auf Basis nachwachsender Rohstoffe, die bedingt durch ihre Aufarbeitung und Eigenschaften nur zu einem gewissen Anteil das petrochemisch basierte Polyol ersetzen können (WO 2009/058367). Die Herstellung von Polyurethanschäumen aus recycelten Polyolen zusammen mit NOPs stellt eine bevorzugte Anwendungsform der Erfindung dar. An important class of optionally usable polyols, which is accessible from natural oils such as palm or soybean oil, so-called "natural oil-based polyols" (NOPs) can be obtained on the basis of renewable raw materials. NOPs are of increasing interest for a more sustainable production of PU foams in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices and has already been described many times in the production of polyurethane foams (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232). A number of these polyols from various manufacturers are now available on the market (WO 2004/020497, US 2006/0229375, WO 2009/058367). Depending on the basic raw material (e.g. soybean oil, palm oil or castor oil) and the subsequent processing, polyols with different properties result. A distinction can essentially be made here between two groups: a) polyols based on renewable raw materials, which are modified to such an extent that they can be used 100% for the production of polyurethanes (WO2004/020497, US2006/0229375); b) polyols based on renewable raw materials which, due to their processing and properties, can only replace the petrochemical-based polyol to a certain extent (WO 2009/058367). The production of polyurethane foams from recycled polyols together with NOPs represents a preferred application of the invention.
Eine weitere Klasse von optional einsetzbaren Polyolen sind solche, die als Prepolymere durch Umsetzung von Polyol mit Isocyanat in einem Molverhältnis von 100 zu 1 bis 5 zu 1 , bevorzugt 50 zu 1 bis 10 zu 1 erhalten werden. A further class of polyols which can optionally be used are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100:1 to 5:1, preferably 50:1 to 10:1.
Noch eine weitere Klasse von optional einsetzbaren Polyolen stellen die sogenannten Füllstoffpolyole (Polymerpolyole) dar. Diese zeichnen sich dadurch aus, dass sie feste organische Füllstoffe bis zu einem Feststoffgehalt von 40 Gew.-% oder mehr in disperser Verteilung enthalten. Man kann z.B. unter anderem verwenden: The so-called filler polyols (polymer polyols) represent yet another class of optionally usable polyols. These are characterized in that they contain solid organic fillers up to a solids content of 40% by weight or more in disperse distribution. For example, you can use:
SAN-Polyole: Dies sind hochreaktive Polyole, welche ein Copolymer auf der Basis Styrol/Acrylnitril (SAN) dispergiert enthalten. SAN polyols: These are highly reactive polyols containing a dispersed styrene/acrylonitrile (SAN)-based copolymer.
PHD-Polyole: Dies sind hochreaktive Polyole, welche Polyharnstoffpartikel in dispergierter Form enthalten. PIPA-Polyole: Dies sind hochreaktive Polyole, welche Polyurethanpartikel in dispergierter Form enthalten, hergestellt beispielsweise durch in situ-Reaktion eines Isocyanats mit einem Alkanolamin in einem konventionellen Polyol. PHD Polyols: These are highly reactive polyols containing polyurea particles in a dispersed form. PIPA Polyols: These are highly reactive polyols containing polyurethane particles in dispersed form, prepared, for example, by the in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
Der Festkörperanteil bei den optionalen Füllstoffpolyolen, der je nach Anwendung bevorzugt zwischen 5 und >40 Gew.-%, bezogen auf das Polyol liegen kann, ist für eine verbesserte Zellöffnung verantwortlich, so dass das Polyol insbesondere mit TDI kontrolliert verschäumbar wird und kein Schrumpfen der Schäume auftritt. Der Festkörper wirkt damit als wesentliche Prozesshilfe. Eine weitere Funktion besteht darin, über den Feststoffanteil die Härte zu kontrollieren, denn höhere Festkörperanteile bewirken eine höhere Härte des Schaums. The solids content of the optional filler polyols, which depending on the application can be between 5 and >40% by weight, based on the polyol, is responsible for improved cell opening, so that the polyol can be foamed in a controlled manner, especially with TDI, and there is no shrinkage of the foaming occurs. The solid thus acts as an essential process aid. Another function is to control the hardness via the solids content, since higher solids content causes the foam to be harder.
Die Formulierungen mit feststoffhaltigen Polyolen sind deutlich weniger eigenstabil und bedürfen daher neben der chemischen Stabilisierung durch die Vernetzungsreaktion eher auch zusätzlich einer physikalischen Stabilisierung.
Weitere optional einsetzbare Polyole sind die sogenannten Zellöffnerpolyole. Diese sind Polyether- Polyole mit einem hohen Ethylenoxidanteil, und zwar vorzugsweise von mindestens 40 Gew.-%, insbesondere von 50 bis 100 Gew.-%, bezogen auf den Gehalt an Alkylenoxid. Ein im Rahmen dieser Erfindung bevorzugtes Verhältnis von Isocyanatkomponente zu Polyolkomponete, ausgedrückt als Index, liegt im Bereich von 10 bis 1000, bevorzugt 40 bis 350. Dieser Index beschreibt das Verhältnis von tatsächlich eingesetzter Menge Isocyanat zurtheoretisch erforderlichen Menge Isocyanat entsprechend einem stöchiometrischen Verhältnis von Isocyanat- Gruppen zu gegenüber Isocyanat reaktiven Gruppen (z.B. OH-Gruppen, NH-Gruppen), multipliziert mit 100. Ein Index von 100 steht für ein molares Verhältnis der reaktiven Gruppen von 1 zu 1.The formulations with polyols containing solids are significantly less inherently stable and therefore require physical stabilization in addition to chemical stabilization through the crosslinking reaction. Other polyols that can optionally be used are the so-called cell opener polyols. These are polyether polyols with a high ethylene oxide content, preferably at least 40% by weight, in particular from 50 to 100% by weight, based on the alkylene oxide content. A ratio of isocyanate component to polyol component that is preferred in the context of this invention, expressed as an index, is in the range from 10 to 1000, preferably 40 to 350. This index describes the ratio of the amount of isocyanate actually used to the theoretically required amount of isocyanate, corresponding to a stoichiometric ratio of isocyanate Groups to isocyanate-reactive groups (e.g. OH groups, NH groups), multiplied by 100. An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
Die Isocyanatkomponente enthält zwingend Recycling-Isocyanat, erhalten nach einem erfindungsgemäßen Verfahren wie zuvor beschrieben. Der Begriff Recycling-Isocyanate umfasst im Sinne der Erfindung Di- und/oder Polyisocyanate erhalten nach einem erfindungsgemäßen Verfahren, wie zuvor beschrieben Dabei entspricht es einer bevorzugten Ausführungsform der Erfindung, wenn der Anteil an Recycling-Isocyanat bezogen auf die insgesamt eingesetzte Isocanatkomponente mehr als 30 Gew,-%, vorzugsweise mehr als 50 Gew.-%, bevorzugt mehr als 70 Gew.-%, weiter bevorzugt mehr als 80 Gew.-%, insbesondere mehr als 95 Gew.-% beträgt. The isocyanate component necessarily contains recycled isocyanate obtained by a process according to the invention as described above. For the purposes of the invention, the term recycled isocyanates includes di- and/or polyisocyanates obtained by a process according to the invention, as described above. It corresponds to a preferred embodiment of the invention if the proportion of recycled isocyanate, based on the total isocyanate component used, is more than 30 % by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 95% by weight.
Als Isocyanatkomponenten werden vorzugsweise ein oder mehrere Isocyanate eingesetzt, die zwei oder mehr Isocyanat-Funktionen aufweisen, wobei die Isocyanatkomponente erfindungsgemäß erhältliches Recycling-Diisocyanat umfasst. Als optional zusätzlich einsetzbare Isocyanate können in dem erfindungsgemäßen Verfahren alle Isocyanate, insbesondere die an sich bekannten aliphatischen, cycloaliphatischen, araliphatischen und vorzugsweise aromatischen mehrwertigen Isocyanate eingesetzt werden. Geeignete Isocyanate im Sinne dieser Erfindung weisen zwei oder mehr Isocyanat-Funktionen auf. One or more isocyanates which have two or more isocyanate functions are preferably used as isocyanate components, the isocyanate component comprising recycled diisocyanate obtainable according to the invention. Any isocyanates, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se, can be used as optionally additionally usable isocyanates in the process according to the invention. Suitable isocyanates for the purposes of this invention have two or more isocyanate functions.
Geeignete Isocyanate im Sinne dieser Erfindung sind vorzugsweise alle mehrfunktionalen organischen Isocyanate, wie z.B. Diphenylmethandiisocyanat (MDI), Toluoldiisocyanat (TDI), Hexamethylendiisocyanat (HMDI) und/oder Isophorondiisocyanat (IPDI). Ebenfalls vorzugsweise einsetzbar ist das als „polymeres MDI“ („crude MDI“ oder Polyphenylpolymethylenpolyisocyanat) bekannte Gemisch aus MDI und höher kondensierten Analogen mit einer mittleren Funktionalität von 2 bis 4. Suitable isocyanates for the purposes of this invention are preferably all polyfunctional organic isocyanates, such as diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and/or isophorone diisocyanate (IPDI). The mixture of MDI and higher-condensed analogues with an average functionality of 2 to 4, known as “polymeric MDI” (“crude MDI” or polyphenylpolymethylene polyisocyanate), can also preferably be used.
Besonders bevorzugt einsetzbar sind 2,4‘-Diphenylmethandiisocyanat und/oder 2,2‘- Diphenylmethandiisocyanat und/oder Polyphenylpolymethylenpolyisocyanat (crude MDI) und/oder 2,4-Toluoldiisocyanat und/oder 2,6-Toluoldiisocyanat oder Mischungen dieser.
Besonders geeignet sind vorzugsweise auch MDI-Prepolymere. Beispiele für besonders geeignete Isocyanate sind z.B. in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951 , EP 1678232 und der WO 2005/085310 aufgeführt, auf die hier in vollem Umfang Bezug genommen wird. Geeignete Katalysatoren, die in dem erfindungsgemäßen Verfahren zur Herstellung von PU-Schaum verwendet werden können, sind vorzugsweise Substanzen, die die Gelreaktion (Isocyanat-Polyol), die Treibreaktion (Isocyanat-Wasser) oder die Di- bzw. Trimerisierung des Isocyanats katalysieren.Particular preference is given to using 2,4'-diphenylmethane diisocyanate and/or 2,2'-diphenylmethane diisocyanate and/or polyphenylpolymethylene polyisocyanate (crude MDI) and/or 2,4-toluene diisocyanate and/or 2,6-toluene diisocyanate or mixtures of these. MDI prepolymers are also particularly suitable. Examples of particularly suitable isocyanates are listed, for example, in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, to which reference is made here in its entirety. Suitable catalysts which can be used in the process according to the invention for producing PU foam are preferably substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the dimerization or trimerization of the isocyanate.
Es entspricht einer bevorzugten Ausführungsform der Erfindung, wenn der eingesetzte Katalysator ausgewählt ist aus Triethylendiamin, 1 ,4-diazabicyclo[2.2.2]octan-2-methanol, Diethanolamin, N-[2-[2-It corresponds to a preferred embodiment of the invention if the catalyst used is selected from triethylenediamine, 1,4-diazabicyclo[2.2.2]octane-2-methanol, diethanolamine, N-[2-[2-
(Dimethylamino)ethoxy]ethyl]-N-methyl-1 ,3-propandiamin, 2-[[2-(2-(Dimethylamino)ethoxy)- ethyl]methylamino]ethanol, 1 ,T-[(3-{bis[3-(dimethylamino)propyl]-amino}propyl)imino]dipropan-2-ol, [3-(Dimethylamino)propyl]harnstoff, 1 ,3-Bis[3-(dimethylamino)propyl]harnstoff und/oder Aminkatalysatoren der allgemeinen Struktur (1 a) und/oder der Struktur (1 b):
(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, 2-[[2-(2-(dimethylamino)ethoxy)-ethyl]methylamino]ethanol, 1,T-[(3-{bis[ 3-(dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, [3-(dimethylamino)propyl]urea, 1,3-bis[3-(dimethylamino)propyl]urea and/or amine catalysts in general Structure (1 a) and/or the structure (1 b):
X umfasst Sauerstoff, Stickstoff, Hydroxyl, Amine der Struktur (NRm oder NRmRlv) oder Harnstoffgruppen (N(RV)C(0)N(RVI) oder N(RV")C(0)NRVIRV") X includes oxygen, nitrogen, hydroxyl, amines of structure (NR m or NR m R lv ) or urea groups (N(R V )C(O)N(R VI ) or N(R V ")C(O)NR VI RV ")
Y umfasst Amine NRVIIIRIX oder Ether ORlx Y includes amines NR VIII R IX or ethers OR lx
RUI umfassen gleiche oder verschiedene lineare oder cyclische, aliphatische oder aromatische Kohlenwasserstoffe mit 1-8 Kohlenstoffatomen die ggf. mit einer OH Gruppe funktionalisiert sind; und/oder umfassen Wasserstoff R UI include identical or different linear or cyclic, aliphatic or aromatic hydrocarbons with 1-8 carbon atoms which are optionally functionalized with an OH group; and/or comprise hydrogen
RIII IX umfassen gleiche oder verschiedene lineare oder cyclische, aliphatische oder aromatische Kohlenwasserstoffe mit 1-8 Kohlenstoffatomen die ggf. mit einer OH Gruppe, einer NH oder einer NH2 Gruppe funktionalisiert sind; und/oder umfassen Wasserstoff m = 0 bis 4, bevorzugt 2 oder 3 n = 2 bis 6, bevorzugt 2 oder 3 i = 0 bis 3, bevorzugt 0-2
Rx umfasst gleiche oder verschiedene Reste bestehend aus Wasserstoff und/oder lineare, verzweigte oder cyclische aliphatische oder aromatische Kohlenwasserstoffe mit 1 - 18 Kohlenstoffatomen, die mit 0 - 1 Hydroxylgruppen und 0 - 1 NH2-Gruppen substituiert sein können. Z umfasst Sauerstoff, N-Rx oder CH2. R III IX include identical or different linear or cyclic, aliphatic or aromatic hydrocarbons with 1-8 carbon atoms which are optionally functionalized with an OH group, an NH or an NH2 group; and/or comprise hydrogen m = 0 to 4, preferably 2 or 3 n = 2 to 6, preferably 2 or 3 i = 0 to 3, preferably 0-2 R x includes identical or different radicals consisting of hydrogen and/or linear, branched or cyclic aliphatic or aromatic hydrocarbons with 1-18 carbon atoms, which can be substituted with 0-1 hydroxyl groups and 0-1 NH 2 groups. Z includes oxygen, NRx or CH2.
Eine weitere Klasse an geeigneten Katalysatoren, die in dem erfindungsgemäßen Verfahren vorzugsweise eingesetzt werden können, sind Metallverbindungen der Metalle Sn, Bi, Zn, AI oder K besonders Sn, Zn oder Bi. Die Metallverbindungen lassen sich dabei in die Untergruppen der metallorganischen Verbindungen, metallorganischen Salze, organischen Metallsalze sowie anorganischen Metallsalze einteilen, die im Folgenden erläutert seien. Another class of suitable catalysts that can preferably be used in the process according to the invention are metal compounds of the metals Sn, Bi, Zn, Al or K, especially Sn, Zn or Bi. The metal compounds can be divided into the subgroups of organometallic compounds, organometallic Classify salts, organic metal salts and inorganic metal salts, which are explained below.
Der Ausdruck „metallorganische oder organometallische Verbindungen“ umfasst im Sinne dieser Erfindung insbesondere den Einsatz metallhaltiger Verbindungen, die über eine direkte Kohlenstoff- Metall-Bindung verfügen, hier auch als Metallorganyle (z.B. Zinnorganyle) oder organometallische bzw. Organometall-Verbindungen (z.B. Organozinn-Verbindungen) bezeichnet. Der Ausdruck „organometallische oder metallorganische Salze“ umfasst im Sinne dieser Erfindung insbesondere den Einsatz von metallorganischen oder organometallischen Verbindungen mit Salzcharakter, das heißt lonenverbindungen, bei denen entweder das Anion oder Kation von metallorganischer Natur ist (z.B. Organozinn-Oxide, Organozinn-Chloride oder Organozinn-Carboxylate). Der Ausdruck „organische Metallsalze“ umfasst im Sinne dieser Erfindung insbesondere den Einsatz von metallhaltigen Verbindungen, die über keine direkte Kohlenstoff-Metall-Bindung verfügen und gleichzeitig Metallsalze sind, bei denen entweder das Anion oder das Kation eine organische Verbindung ist (z.B. Zinn(ll)-Carboxylate). Der Ausdruck „anorganische Metallsalze“ umfasst im Sinne dieser Erfindung insbesondere den Einsatz von metallhaltigen Verbindungen oder von Metallsalzen, bei denen weder Anion noch Kation eine organische Verbindung ist, z.B. Metall- Chloride (z.B. Zinn(ll)-Chlorid). For the purposes of this invention, the term “organometallic or organometallic compounds” includes, in particular, the use of metal-containing compounds that have a direct carbon-metal bond, here also as organometallic compounds (e.g. organotin compounds) or organometallic or organometallic compounds (e.g. organotin compounds). ) designated. For the purposes of this invention, the term “organometallic or organometallic salts” includes in particular the use of organometallic or organometallic compounds with a salt character, i.e. ionic compounds in which either the anion or cation is of an organometallic nature (e.g. organotin oxides, organotin chlorides or organotin -carboxylates). In the context of this invention, the expression "organic metal salts" includes in particular the use of metal-containing compounds that do not have a direct carbon-metal bond and are at the same time metal salts in which either the anion or the cation is an organic compound (e.g. tin(II )-carboxylates). In the context of this invention, the expression "inorganic metal salts" includes in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, e.g. metal chlorides (e.g. tin(II) chloride).
Geeignete einsetzbare organische und metallorganische Metallsalze enthalten vorzugsweise Alkoholat-, Mercaptat- oder Carboxylat-Anionen wie z.B. Acetat, 2-Ethyl-hexanoat, Octanoat, Isononanoat, Decanoat, Neodecanoat, Ricinoleat, Laurat und oder Oleat besonders bevorzugt 2- Ethyl-hexanoat, Ricinoleat, Neodecanoat oder Isononanoat. Geeignete einsetzbare metallhaltige Katalysatoren werden in der Regel vorzugsweise so ausgewählt, dass sie keinen störenden Eigengeruch aufweisen, toxikologisch im Wesentlichen unbedenklich sind und dass die resultierenden Polyurethansysteme, insbesondere Polyurethanschäume möglichst geringe Katalysator-bedingte Emissionen aufweisen.
Es kann bevorzugt sein eine oder mehrere Metallverbindungen mit einem oder mehreren Aminkatalysatoren der Formel (1a) und/oder (1 b) zu kombinieren. Suitable organic and organometallic metal salts that can be used preferably contain alcoholate, mercaptate or carboxylate anions such as, for example, acetate, 2-ethylhexanoate, octanoate, isononanoate, decanoate, neodecanoate, ricinoleate, laurate and/or oleate, particularly preferably 2-ethylhexanoate, ricinoleate , neodecanoate or isononanoate. Suitable metal-containing catalysts that can be used are generally preferably selected such that they have no objectionable intrinsic odor, are essentially toxicologically harmless and that the resulting polyurethane systems, in particular polyurethane foams, have the lowest possible catalyst-related emissions. It may be preferred to combine one or more metal compounds with one or more amine catalysts of formula (1a) and/or (1b).
Bei der erfindungsgemäßen Herstellung von Polyurethanschaumstoffen kann es bevorzugt sein, die Verwendung von metallorganischen Salzen wie zum Beispiel von Dibutylzinndilaurat auszuschließen. In the production of polyurethane foams according to the present invention, it may be preferred to exclude the use of organometallic salts such as dibutyltin dilaurate.
Geeignete Einsatzmengen an Katalysatoren im erfindungsgemäßen Verfahren richten sich nach dem Typ des Katalysators und liegen vorzugsweise im Bereich von 0,01 bis 5 pphp (= Gewichtsteilen bezogen auf 100 Gewichtsteile Polyol) bzw. 0,1 bis 10 pphp für Kaliumsalze. Suitable amounts of catalysts in the process according to the invention depend on the type of catalyst and are preferably in the range from 0.01 to 5 pphp (=parts by weight based on 100 parts by weight polyol) or 0.1 to 10 pphp for potassium salts.
Geeignete Wasser-Gehalte im erfindungsgemäßen Verfahren hängen davon ab, ob zusätzlich zum Wasser noch physikalische Treibmittel eingesetzt werden oder nicht. Bei rein Wasser-getriebenen Schäumen liegen die Werte bei vorzugsweise 1 bis 20 pphp, werden zusätzlich andere Treibmittel eingesetzt, verringert sich die Einsatzmenge auf üblicherweise z.B. 0 oder z.B. 0,1 bis 5 pphp. Zur Erlangung hoher Schaumraumgewichte werden vorzugsweise weder Wasser noch andere Treibmittel eingesetzt. Geeignete optional einsetzbare physikalische Treibmittel im Sinne dieser Erfindung sind Gase, beispielsweise verflüssigtes CO2, und leichtflüchtige Flüssigkeiten, beispielsweise Kohlenwasserstoffe mit 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffe, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, aber auch olefinische Fluorkohlenwasserstoffe wie HHO 1233zd oder HH01336mzzZ, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141b, Sauerstoff-haltige Verbindungen wie Methylformiat und Dimethoxymethan, oder Chlorkohlenwasserstoffe, bevorzugt Dichlormethan und 1 ,2-Dichlorethan. Des Weiteren eignen sich Ketone (z.B. Aceton) oder Aldehyde (z.B. Methylal) als Treibmittel. Suitable water contents in the process according to the invention depend on whether or not physical blowing agents are used in addition to the water. In the case of purely water-blown foams, the values are preferably from 1 to 20 pphp, but if other blowing agents are also used, the amount used is usually reduced to, for example, 0 or, for example, 0.1 to 5 pphp. In order to achieve high foam density, preferably neither water nor other blowing agents are used. Suitable physical blowing agents that can optionally be used in the context of this invention are gases, for example liquefied CO2, and volatile liquids, for example hydrocarbons with 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, but also olefinic fluorocarbons such as HHO 1233zd or HH01336mzzZ, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane. Furthermore, ketones (e.g. acetone) or aldehydes (e.g. methylal) are suitable as blowing agents.
Neben oder an Stelle von Wasser und ggf. physikalischen Treibmitteln, können auch andere chemische Treibmittel, die mit Isocyanaten unter Gasentwicklung reagieren, wie beispielsweise Ameisensäure, Carbamate oder Carbonate in der erfindungsgemäßen Additivzusammensetzung vorhanden sein. In addition to or instead of water and, if appropriate, physical blowing agents, other chemical blowing agents which react with isocyanates with evolution of gas, such as formic acid, carbamates or carbonates, can also be present in the additive composition according to the invention.
Als Schaumstabilisatoren (im Sinne der Erfindung auch kurz Stabilisatoren genannt) können die im Stand der Technik genannten Substanzen verwendet werden. Vorteilhafterweise können die erfindungsgemäßen Zusammensetzungen ein oder mehrere Stabilisatoren enthalten. Dabei handelt es sich insbesondere um Kohlenstoffatome aufweisende Siliziumverbindungen, vorzugsweise ausgewählt aus den Polysiloxanen, Polydimethylsiloxanen, organomodifizierten Polysiloxanen, polyethermodifizierten Polysiloxanen und Polyether-Polysiloxan-Copolymeren. Bevorzugte Siliziumverbindungen werden durch Formel (1c) beschrieben: The substances mentioned in the prior art can be used as foam stabilizers (also called stabilizers for short within the meaning of the invention). Advantageously, the compositions of the invention may contain one or more stabilizers. These are in particular silicon compounds having carbon atoms, preferably selected from the polysiloxanes, polydimethylsiloxanes, organomodified polysiloxanes, polyether-modified polysiloxanes and polyether-polysiloxane copolymers. Preferred silicon compounds are described by formula (1c):
Formel (1 c): [R1 2R2SiOi/2]a [R13SiOi/2] [R1 2Si02/2]c [R1R2Si02/2]d [R3Si03/2]e [Si04/2]f Gg mit a = 0 bis 12, bevorzugt 0 bis 10, besonders bevorzugt 0 bis 8
b = 0 bis 8, bevorzugt 0 bis 6, besonders bevorzugt 0 bis 2 c = 0 bis 250, bevorzugt 1 bis 200, besonders bevorzugt 1 ,5 bis 150 d = 0 bis 40, bevorzugt 0 bis 30, besonders bevorzugt 0 bis 20 e = 0 bis 10, bevorzugt 0 bis 8, besonders bevorzugt 0 bis 6 f = 0 bis 5, bevorzugt 0 bis 3, besonders bevorzugt 0 g = 0 bis 3, bevorzugt 0 bis 2,5, besonders bevorzugt 0 bis 2 wobei: a+b+c+d+e+f+g > 3 a + b > 2 Formula (1 c): [R 1 2 R 2 SiOi/ 2 ]a [R 1 3SiOi/ 2 ] [R 1 2 Si0 2/2 ] c [R 1 R 2 Si0 2/2 ] d [R 3 Si0 3 /2 ]e [Si0 4/2 ] f G g with a = 0 to 12, preferably 0 to 10, particularly preferably 0 to 8 b=0 to 8, preferably 0 to 6, particularly preferably 0 to 2 c=0 to 250, preferably 1 to 200, particularly preferably 1.5 to 150 d=0 to 40, preferably 0 to 30, particularly preferably 0 to 20 e = 0 to 10, preferably 0 to 8, particularly preferably 0 to 6 f = 0 to 5, preferably 0 to 3, particularly preferably 0 g = 0 to 3, preferably 0 to 2.5, particularly preferably 0 to 2 where: a+b+c+d+e+f+g > 3 a + b > 2
G = unabhängig voneinander die gleichen oder verschiedene Radikale aus (Ol/2)nSiR1m - CH2CHR5 - R4 - CHR5CH2 - SiR1m(Ol/2)n (Oi/2)nSiR1m - CH2CHR5 - R4 - CR5=CH2 (Oi/2)nSiR1m - CH2CHR5 - R4 - CR5=CR5-CH3 G = independently the same or different radicals from (Ol/ 2 )nSiR 1 m - CH2CHR 5 - R 4 - CHR 5 CH 2 - SiR 1 m(Ol/ 2 )n (Oi/ 2 ) n SiR 1 m - CH 2 CHR 5 - R 4 - CR 5 =CH 2 (Oi/ 2 ) n SiR 1 m - CH 2 CHR 5 - R 4 - CR 5 =CR 5 -CH 3
R4 = unabhängig voneinander die gleichen oder verschiedene divalente organische Radikale, bevorzugt zweifache organische Radikale aus 1 bis 50 Kohlenstoffatomen, optional unterbrochen durch Ether-, Ester- oder Amid-Gruppen und optional mit OH- Gruppen funktionalisiert, oder (-SiR1 20-)xSiR1 2- Gruppen, besonders bevorzugt die gleichen oder verschiedene divalente organische Radikale aus 2 bis 30 Kohlenstoffatomen, optional unterbrochen durch Ether-, Ester- oder Amid-Gruppen und optional mit OH-Gruppen funktionalisiert, oder (-SiR1 20-)xSiR1 2- Gruppen x = 1 bis 50, bevorzugt 1 bis 25, besonders bevorzugt 1 bis 10 R 4 = independently the same or different divalent organic radicals, preferably double organic radicals of 1 to 50 carbon atoms, optionally interrupted by ether, ester or amide groups and optionally functionalized with OH groups, or (-SiR 1 2 0 -) x SiR 1 2 - groups, particularly preferably the same or different divalent organic radicals of 2 to 30 carbon atoms, optionally interrupted by ether, ester or amide groups and optionally functionalized with OH groups, or (-SiR 1 2 0-) x SiR 1 2 - groups x = 1 to 50, preferably 1 to 25, particularly preferably 1 to 10
R5 = unabhängig voneinander die gleichen oder verschiedene Alkylradikale bestehend aus 1 bis 16 Kohlenstoffatomen, Arylradikale mit 6 bis 16 Kohlenstoffatomen oder Wasserstoff, bevorzugt aus der Gruppe der Alkylradikale mit 1 bis 6 Kohlenstoffatomen oder Arylradikale mit 6 bis 10 Kohlenstoffatomen oder Wasserstoff, besonders bevorzugt Methyl oder Wasserstoff. wobei: n = 1 oder 2 m = 1 oder 2 n + m = 3
R1 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 bis 16 Kohlenstoffatomen oder Wasserstoff oder -OR6, bevorzugt Methyl, Ethyl, Octyl, Dodecyl, Phenyl oder Wasserstoff, besonders bevorzugt Methyl oder Phenyl. R2 = unabhängig voneinander gleiche oder verschiedene Polyether erhältlich durch dieR 5 = independently the same or different alkyl radicals consisting of 1 to 16 carbon atoms, aryl radicals having 6 to 16 carbon atoms or hydrogen, preferably from the group of alkyl radicals having 1 to 6 carbon atoms or aryl radicals having 6 to 10 carbon atoms or hydrogen, particularly preferably methyl or hydrogen. where: n = 1 or 2 m = 1 or 2 n + m = 3 R 1 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms or hydrogen or -OR 6 , preferably methyl, ethyl, octyl, dodecyl, phenyl or hydrogen, particularly preferred methyl or phenyl. R 2 = independently identical or different polyethers obtainable through the
Polymerisation von Ethylenoxid und/oder Propylenoxid und/oder anderen Alkylenoxiden wie zum Beispiel Butylenoxid oder Styroloxid mit der generellen Formel (2) oder ein organisches Radikal entsprechend der Formel (3) Polymerization of ethylene oxide and/or propylene oxide and/or other alkylene oxides such as butylene oxide or styrene oxide having the general formula (2) or an organic radical corresponding to the formula (3)
(2) - (R7)h - O - [C2H40]i - [CsHeOJj - [CR8 2CR8 20]k - R9 (3) - Oh - R10 wobei h = 0 oder 1 (2) - (R 7 ) h - O - [C 2 H 4 0]i - [CsHeOJj - [CR 8 2 CR 8 2 0] k - R 9 (3) - Oh - R 10 where h = 0 or 1
R7 = divalentes organisches Radikal, bevorzugt divalentes organisches Alkyl- oder Arylradikal optional substituiert mit -OR6, besonders bevorzugt ein divalentes organisches Radikal des Typs CPH2p. i = 0 bis 150, bevorzugt 1 bis 100, besonders bevorzugt 1 bis 80 j = 0 bis 150, bevorzugt 0 bis 100, besonders bevorzugt 0 bis 80 k = 0 bis 80, bevorzugt 0 bis 40, besonders bevorzugt 0 p = 1 - 18, bevorzugt, 1 - 10, besonders bevorzugt 3 oder 4 wobei i + j + k > 3 R 7 = divalent organic radical, preferably divalent organic alkyl or aryl radical optionally substituted with -OR 6 , more preferably a divalent organic radical of the type C P H 2p . i = 0 to 150, preferably 1 to 100, particularly preferably 1 to 80 j = 0 to 150, preferably 0 to 100, particularly preferably 0 to 80 k = 0 to 80, preferably 0 to 40, particularly preferably 0 p = 1 - 18, preferably 1 - 10, particularly preferably 3 or 4 where i + j + k > 3
R3 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale potentiell substituiert mit Heteroatomen, bevorzugt gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16 Kohlenstoffatomen potentiell substituiert mit Halogenatomen, besonders bevorzugt Methyl, Vinyl, Chlorpropyl oder Phenyl. R 3 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals potentially substituted with heteroatoms, preferably identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms potentially substituted with Halogen atoms, particularly preferably methyl, vinyl, chloropropyl or phenyl.
R6 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16 Kohlenstoffatome oder Wasserstoff, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 - 8 Kohlenstoffatomen oder Wasserstoff, besonders bevorzugt sind Methyl, Ethyl, Isopropyl oder Wasserstoff.
R8 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der Alkylradikale mit 1 bis 18 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen und potentiell substituiert mit Heteroatomen wie Halogenatomen, Arylradikale mit 6 - 18 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen, oder Wasserstoff, bevorzugt Alkylradikale mit 1 bis 12 Kohlenstoffatomen potentiell substituiert mit Etherfunktionen und potentiell substituiert mit Heteroatomen wie Halogenatomen oder Arylradikale mit 6 bis 12 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen, oder Wasserstoff, besonders bevorzugt Methyl, Ethyl, Benzyl oder Wasserstoff. R 6 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms or hydrogen, preferably saturated or unsaturated alkyl radicals having 1 to 8 carbon atoms or hydrogen, methyl, ethyl being particularly preferred , isopropyl or hydrogen. R 8 = identical or different radicals selected from the group of alkyl radicals with 1 to 18 carbon atoms, potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms, aryl radicals with 6 - 18 carbon atoms, potentially substituted with ether functions, or hydrogen, preferably alkyl radicals with 1 to 12 carbon atoms potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms or aryl radicals having 6 to 12 carbon atoms potentially substituted with ether functions, or hydrogen, more preferably methyl, ethyl, benzyl or hydrogen.
R9= gleiche oder verschiedene Radikale ausgewählt aus der Gruppe Wasserstoff, Alkyl, - C(0)-R11, -C(0)0-R11 oder-C(0)NHR11, gesättigt oder ungesättigt, optionaler Weise substituiert mit Heteroatomen, bevorzugt Wasserstoff oder Alkylradikale mit 1 bis 8 Kohlenstoffatomen oder Acetyl-, besonders bevorzugt Wasserstoff, Acetyl, Methyl oder Butyl. R 9 = same or different radicals selected from the group hydrogen, alkyl, -C(0)-R 11 , -C(0)0-R 11 or -C(0)NHR 11 , saturated or unsaturated, optionally substituted with Heteroatoms, preferably hydrogen or alkyl radicals having 1 to 8 carbon atoms or acetyl, particularly preferably hydrogen, acetyl, methyl or butyl.
R10 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale oder Arylradikale, potentiell substituiert mit einem oder mehreren OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 bis 18 Kohlenstoffatomen oder Arylradikale mit 6 - 18 Kohlenstoffatomen, optional substituiert mit einem oder mehreren OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten, besonders bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 bis 18 Kohlenstoffatomen oder Arylradikale mit 6 - 18R 10 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals or aryl radicals, potentially substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, preferably saturated or unsaturated alkyl radicals with 1 to 18 Carbon atoms or aryl radicals with 6 - 18 carbon atoms optionally substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, more preferably saturated or unsaturated alkyl radicals with 1 to 18 carbon atoms or aryl radicals with 6 - 18
Kohlenstoffatomen substituiert mit mindestens einem OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten. Carbon atoms substituted with at least one OH, ether, epoxide, ester, amine and/or halogen substituent.
R11 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16 Kohlenstoffatomen, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 - 8 Kohlenstoffatomen oder Arylradikale mitR 11 = identical or different radicals selected from the group consisting of alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16 carbon atoms, preferably saturated or unsaturated alkyl radicals having 1 to 8 carbon atoms or aryl radicals
6 - 12 Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, Butyl oder Phenyl. 6 - 12 carbon atoms, particularly preferably methyl, ethyl, butyl or phenyl.
Die Schaumstabilisatoren aus Formel (1c) können vorzugsweise in organischen Lösungsmitteln wie zum Beispiel Dipropylenglycol, Polyether-Alkoholen oder Polyether-Diolen abgemischt in PU Systemen eingesetzt werden. In Fall von Mischungen von Stabilisatoren der Formel (1c) kann zusätzlich vorzugsweise ein Kompatibilisator eingesetzt werden. Dieser kann ausgewählt sein aus der Gruppe aliphatischer oder aromatischer Kohlenwasserstoffe, besonders bevorzugt aliphatische Polyether oder Polyester.The foam stabilizers of the formula (1c) can be used in PU systems, preferably mixed in organic solvents such as, for example, dipropylene glycol, polyether alcohols or polyether diols. In the case of mixtures of stabilizers of the formula (1c), a compatibilizer can preferably also be used. This can be selected from the group of aliphatic or aromatic hydrocarbons, particularly preferably aliphatic polyethers or polyesters.
Als ein oder mehrere Kohlenstoffatome aufweisende Siliziumverbindungen können vorzugsweise die im Stand der Technik genannten Substanzen verwendet werden. Vorzugsweise werden solche Si-Verbindungen eingesetzt, die für den jeweiligen Schaumtypen besonders geeignet sind. Geeignete Siloxane sind beispielsweise in den folgenden Schriften beschrieben: EP 0839852, EP 1544235, DE 102004001408, WO 2005/118668, US 2007/0072951 , DE 2533074, EP 1537159 EP
533202, US 3933695, EP 0780414, DE 4239054, DE 4229402, EP 867465. Die Herstellung der Si- Verbindungen kann wie im Stand der Technik beschrieben erfolgen. Geeignete Beispiele sind z. B. in US 4147847, EP 0493836 und US 4855379 beschrieben. The substances mentioned in the prior art can preferably be used as silicon compounds having one or more carbon atoms. Those Si compounds which are particularly suitable for the particular type of foam are preferably used. Suitable siloxanes are described, for example, in the following documents: EP 0839852, EP 1544235, DE 102004001408, WO 2005/118668, US 2007/0072951, DE 2533074, EP 1537159 EP 533202, US 3933695, EP 0780414, DE 4239054, DE 4229402, EP 867465. The Si compounds can be prepared as described in the prior art. Suitable examples are e.g. e.g. in US 4147847, EP 0493836 and US 4855379.
Vorzugsweise können von 0,00001 bis 20 Massenteile Schaumstabilisatoren, insbesondere Siliziumverbindungen, pro 100 Massenteile Polyolkomponenten eingesetzt werden. Preferably, from 0.00001 to 20 parts by mass of foam stabilizers, in particular silicon compounds, can be used per 100 parts by mass of polyol components.
Als weitere optionale Zusatzstoffe können alle nach dem Stand der Technik bekannten Substanzen verwendet werden, die bei der Herstellung von Polyurethanen, insbesondere von Polyurethanschaumstoffen, Verwendung finden, wie zum Beispiel Treibmittel, vorzugsweise Wasser zur Bildung von CO2 und, falls nötig, weitere physikalische Treibmittel, Flammschutzmittel, Puffersubstanzen, Tenside, Biozide, Farbstoffe, Pigmente, Füllstoffe, Antistatik-Additive, Vernetzer, Kettenverlängerer, Zellöffner wie z.B. beschrieben in EP 2998333A1 , Nukleierungsmittel, Verdicker, Duftstoffe, Zellvergröberer wie z.B. beschrieben in EP 2986661 B1 , Weichmacher, Härtevermittler, Additive für die Verhinderung von Cold Flow wie z.B. beschrieben in DE 2507161C3, WO 2017029054A1 , Aldehydfänger wie z.B. beschrieben in WO 2021/013607 A1 , Additive für Beständigkeit von PU-Schäumen gegenüber Hydrolyse wie z.B. beschrieben in USAll substances known from the prior art which are used in the production of polyurethanes, in particular polyurethane foams, can be used as further optional additives, such as blowing agents, preferably water to form CO2 and, if necessary, other physical blowing agents Flame retardants, buffer substances, surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers as described, for example, in EP 2998333A1, nucleating agents, thickeners, fragrances, cell coarsening agents, as described, for example, in EP 2986661 B1, plasticizers, hardeners, additives for preventing cold flow as described, for example, in DE 2507161C3, WO 2017029054A1, aldehyde scavengers as described, for example, in WO 2021/013607 A1, additives for the resistance of PU foams to hydrolysis, as described, for example, in US
2015/0148438A1 , Kompatibilisatoren (Emulgatoren), Adhäsionsvermittler, Hydrophobierungs-Additive, Flammlaminierungs-Additive wie z.B. beschrieben in EP 2292677B1 , Druckverformungsrest vermindernde Additive, Geruchsverminderer und/oder zusätzliche katalytisch aktive Substanzen, insbesondere wie oben definiert. Als optional einsetzbare Vernetzer und optionale einsetzbare Kettenverlängerer werden niedermolekulare, gegenüber Isocyanaten reaktive, mehrfunktionelle Verbindungen bezeichnet. Geeignet sind zum Beispiel Hydroxyl- oder Amin-terminierte Substanzen wie Glycerin, Neopentylglycol, Dipropylenglycol, Zuckerverbindungen, 2-Methyl-1 ,3-propandiol, Triethanolamin (TEOA), Diethanolamin (DEOA) und Trimethylolpropan. Ebenfalls einsetzbare Vernetzer sind polyethoxylierte und/oder polypropoxylierte Glycerin- oder Zuckerverbindungen deren zahlenmittleres Molekulargewicht unterhalb von 1500 g/mol liegt. Die optionale Einsatzkonzentration liegt vorzugsweise zwischen 0,1 und 5 Teilen, bezogen auf 100 Teile Polyol, kann aber je nach Formulierung auch davon abweichen. Bei der Verwendung von crude MDI bei der Formverschäumung übernimmt dies ebenfalls eine vernetzende Funktion. Der Gehalt an niedermolekularen Vernetzern kann daher bei steigender Menge an crude MDI entsprechend reduziert werden. 2015/0148438A1, compatibilizers (emulsifiers), adhesion promoters, hydrophobing additives, flame lamination additives as described, for example, in EP 2292677B1, compression set-reducing additives, odor reducers and/or additional catalytically active substances, in particular as defined above. Crosslinkers that can be used as an option and chain extenders that can be used as an option are low molecular weight, polyfunctional compounds that are reactive toward isocyanates. For example, hydroxyl- or amine-terminated substances such as glycerol, neopentyl glycol, dipropylene glycol, sugar compounds, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane are suitable. Crosslinkers that can also be used are polyethoxylated and/or polypropoxylated glycerol or sugar compounds whose number-average molecular weight is below 1500 g/mol. The optional use concentration is preferably between 0.1 and 5 parts, based on 100 parts of polyol, but can also deviate from this depending on the formulation. When using crude MDI for foam molding, this also takes on a crosslinking function. The content of low-molecular crosslinkers can therefore be correspondingly reduced as the amount of crude MDI increases.
Geeignete optionale Stabilisatoren gegen oxidativen Abbau, so genannte Antioxidantien, sind vorzugs-weise alle gängigen Radikalfänger, Peroxidfänger, UV-Absorber, Lichtstabilisatoren, Komplexbildner für Metallionenverunreinigungen (Metalldeaktivatoren). Bevorzugt einsetzbar sind Verbindungen folgender Substanzklassen, bzw. Substanzklassen enthaltend folgende funktionelle Gruppen: 2-(2‘-Hydroxyphenyl)benzotriazole, 2-Hydroxybenzophenone, Benzoesäuren und Benzoate, Phenole, insbesondere enthaltend tert-Butyl- und oder Methylsubstituenten am Aromaten,
Benzofuranone, Diarylamine, Triazine, 2,2,6,6-Tetramethylpiperidine, Hydroxylamine, Alkyl- und Arylphosphite, Sulfide, Zinkcarboxylate, Diketone. Suitable optional stabilizers against oxidative degradation, so-called antioxidants, are preferably all common free-radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators). Compounds of the following classes of substances, or classes of substances containing the following functional groups, can preferably be used: 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acids and benzoates, phenols, in particular containing tert-butyl and/or methyl substituents on the aromatic compound, Benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones.
Geeignete optionale Flammschutzmittel im Sinne dieser Erfindung sind alle Substanzen, die nach dem Stand der Technik als dafür geeignet betrachtet werden. Bevorzugte Flammschutzmittel sind beispielsweise flüssige organische Phosphor-Verbindungen, wie halogenfreie organische Phosphate, z.B. Triethylphosphat (TEP), halogenierte Phosphate, z.B. Tris(1-chlor-2- propyl)phosphat (TCPP), Tris(1 ,3-dichlorisopropyl)phosphat (TDCPP) und Tris(2- chlorethyl)phosphat (TCEP) und organische Phosphonate, z.B. Dimethylmethanphosphonat (DMMP), Dimethylpropanphosphonat (DMPP), oder Oligomere Ethyl-ethylene-phosphate oder Feststoffe wie Ammoniumpolyphosphat (APP) und roter Phosphor. Des Weiteren sind als Flammschutzmittel halogenierte Verbindungen, beispielsweise halogenierte Polyole, sowie Feststoffe wie Blähgraphit und Melamin geeignet. Suitable optional flame retardants for the purposes of this invention are all substances which are considered suitable according to the prior art. Preferred flame retardants are, for example, liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, e.g. tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloroisopropyl) phosphate ( TDCPP) and tris(2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. dimethyl methane phosphonate (DMMP), dimethyl propane phosphonate (DMPP), or oligomers ethyl ethylene phosphates or solids such as ammonium polyphosphate (APP) and red phosphorus. Halogenated compounds, for example halogenated polyols, and solids such as expandable graphite and melamine are also suitable as flame retardants.
Durch das erfindungsgemäße Verfahren können jegliche Polyurethanschäume hergestellt werden. Die Bezeichnung Polyurethan ist im Sinne der Erfindung insbesondere als Oberbegriff für ein aus Di- bzw. Polyisocyanaten und Polyolen oder anderen gegenüber Isocyanat reaktive Spezies, wie z.B. Aminen, hergestelltes Polymer zu verstehen, wobei die Urethan-Bindung nicht ausschließlicher oder überwiegender Bindungstyp sein muss. Auch Polyisocyanurate und Polyharnstoffe sind ausdrücklich mit eingeschlossen. Any type of polyurethane foam can be produced by the process according to the invention. For the purposes of the invention, the term polyurethane is to be understood in particular as a generic term for a polymer made from di- or polyisocyanates and polyols or other species that are reactive towards isocyanate, such as amines, for example, where the urethane bond does not have to be the exclusive or predominant type of bond. Polyisocyanurates and polyureas are also expressly included.
Die erfindungsgemäße Herstellung von Polyurethanschaumstoffen kann nach allen dem Fachmann geläufigen Verfahren erfolgen, beispielsweise im Handmischverfahren oder bevorzugt mit Hilfe von Hochdruck- oder Niederdruck-Verschäumungsmaschinen. Das erfindungsgemäße Verfahren kann kontinuierlich oder diskontinuierlich durchgeführt werden. Eine diskontinuierliche Durchführung des Verfahrens ist bevorzugt bei der Herstellung von Formschäumen, Kühlschränken, Schuhsohlen oder Paneelen. Eine kontinuierliche Verfahrensführung ist bei der Herstellung von Dämmplatten, Metallverbundelementen, Blöcken oder bei Sprühverfahren bevorzugt. The production of polyurethane foams according to the invention can be carried out by any method familiar to the person skilled in the art, for example by hand mixing or preferably with the aid of high-pressure or low-pressure foaming machines. The process according to the invention can be carried out continuously or batchwise. A discontinuous implementation of the method is preferred in the production of molded foams, refrigerators, shoe soles or panels. A continuous procedure is preferred in the production of insulating panels, metal composite elements, blocks or spray processes.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Polyurethanschaum, vorzugsweise PU- Hartschaum, PU-Weichschaum, PU-Heißweichschaum (Standard-Schaum), viskoelastischer PU- Schaum, HR-PU-Schaum, PU-Hypersoft-Schaum, halbharter PU-Schaum, thermoverformbarer PU- Schaum oder PU-lntegralschaum, bevorzugt PU-Heißweichschaum, HR-PU-Schaum, PU- Hypersoft-Schaum oder viskoelastischer PU-Schaum, hergestellt gemäß einem erfindungsgemäßen Verfahren wie zuvor beschrieben. PU-Heißweichschäume sind am meisten bevorzugt. Another object of the present invention is a polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam (standard foam), viscoelastic PU foam, HR PU foam, PU hypersoft foam, semi-rigid PU foam, thermoformable PU foam or PU integral foam, preferably PU hot flexible foam, HR PU foam, PU hypersoft foam or viscoelastic PU foam, produced according to a method according to the invention as described above. PU hot flexible foams are most preferred.
Ein ganz besonders bevorzugter Polyurethanweichschaumstoff im Sinne dieser Erfindung weist insbesondere die folgende Zusammensetzung auf: A very particularly preferred flexible polyurethane foam for the purposes of this invention has the following composition in particular:
Komponente Gewichtsanteile (pphp) Polyol 100 Component parts by weight (pphp) Polyol 100
(Amin-)Katalysator 0,01 bis 5
Zinn-Katalysator 0 bis 5, vorzugsweise 0,001 bis 2(amine) catalyst 0.01 to 5 Tin catalyst 0 to 5, preferably 0.001 to 2
Siloxan 0,1 bis 15, vorzugsweise 0,2 bis 7Siloxane 0.1 to 15, preferably 0.2 to 7
Wasser 0 bis < 15, vorzugsweise 0,1 bis 10Water 0 to <15, preferably 0.1 to 10
Weitere Treibmittel 0 bis 130 Flammschutzmittel 0 bis 70 Füllstoffe 0 bis 150 weitere Additive 0 bis 20 Other blowing agents 0 to 130 Flame retardants 0 to 70 Fillers 0 to 150 Other additives 0 to 20
Isocyanat, umfassend Recycling-Isocyanat Isocyanat-Index: größer 50 Isocyanate, including recycled isocyanate Isocyanate index: greater than 50
Die erfindungsgemäßen Polyurethanschäume können z. B. als Kühlschrankisolierung, Dämmplatte, Sandwichelement, Rohrisolation, Sprühschaum, 1- & 1 ,5-Komponenten-Dosenschaum (ein 1 ,5- Komponenten-Dosenschaum ist ein Schaum der durch zerstören eines Behälters in der Dose erzeugt wird), Holzimitat, Modellschaum, Verpackungsschaum, Matratze, Möbelpolster, Automobil- Sitzpolster, Kopfstütze, Instrumententafel, Automobil-Innenverkleidung, Automobil-Dachhimmel, Schallabsorptionsmaterial, Lenkrad, Schuhsole, Teppichrückseitenschaum, Filterschaum, Dichtschaum, Dichtmittel, Kleber, Bindemittel, Lackierung oder als Beschichtung oder zur Herstellung entsprechender Produkte verwendet werden. Dies entspricht einem weiteren Gegenstand der Erfindung. The polyurethane foams according to the invention can, for. B. as refrigerator insulation, insulating board, sandwich element, pipe insulation, spray foam, 1 & 1.5 component can foam (a 1.5 component can foam is a foam that is produced by destroying a container in the can), imitation wood, model foam , packaging foam, mattress, furniture pad, automotive seat pad, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant, adhesive, binder, paint or as a coating or to manufacture related products be used. This corresponds to a further object of the invention.
Beispiele: Examples:
Herstellung des erfindungsgemäßen Recycling-Toluoldiisocyanats Production of the recycling toluene diisocyanate according to the invention
Das erfindungsgemäße Recycling-Toluoldiisocyanat wurde erhalten durch die Hydrolyse von Polyurethan in Anwesenheit einer gesättigten K2C03-Lösung und Tetrabutylammoniumhydrogensulfat als Katalysator und anschließender Phosgenierung des isolierten Toluoldiamingemisch: The recycling toluene diisocyanate according to the invention was obtained by the hydrolysis of polyurethane in the presence of a saturated K2C03 solution and tetrabutylammonium hydrogen sulfate as catalyst and subsequent phosgenation of the isolated toluenediamine mixture:
Ein Reaktor der Firma Parr (Parr Instrumental Company) ausgestattet mit einem PTFE- Innenbehälter und einem mechanischen Rührer wurde mit 25 g komprimierten Schaumstücken (ca. 1 cm x 1 cm) befüllt. Der verwendete Polyurethanschaum wurde gemäß der unten aufgeführtenA Parr reactor (Parr Instrumental Company) equipped with a PTFE inner vessel and a mechanical stirrer was charged with 25 g of compressed foam pieces (ca. 1 cm×1 cm). The polyurethane foam used was according to the one listed below
Formulierung 1 hergestellt. Anschließend wurden 75 g gesättigte K2CC>3-Lösung (pKb-Wert 3,67 bei 25 °C) hinzugegeben. Daraufhin wurde der Katalysator Tetrabutylammoniumhydrogensulfat zu 5 Gew.-% bezogen auf die Masse des Reaktionsgemisches zugesetzt. Der Reaktor wurde
verschlossen und das Reaktionsgemisch wurde für 14 Stunden auf eine Innen-Temperatur von 150 °C erhitzt. Nach Abschluss der 14 Stunden wurde das Heizen beendet und das Reaktionsgemisch wurde auf Raumtemperatur abgekühlt. Nach Öffnen des Reaktors wurde das Reaktionsgemisch in einen Rundkolben überführt. Das Wasser wurde über Rotationsverdampfung entfernt und die zurückbleibende Reaktionsmischung mit Cyclohexan extrahiert und anschließend filtriert. Der abfiltrierte Feststoff wurde mit Toluol extrahiert und die erhaltene Extraktionslösung getrocknet. Nach Entfernen des Toluols über Rotationsverdampfung wurde das Toluoldiamin als Isomerengemisch erhalten. Zur Umsetzung zum Isocyanat wurden 24 g des Toluoldiamin in 1 ,2 L Toluol gelöst. Anschließend wurden 250 ml_ einer 0,157 molaren Lösung von Triphosgen in Toluol tropfenweise zudosiert. Nach vollständiger Zugabe wurde die Reaktionsmischung auf 110 °C erhitzt und für 2 h bei dieser Temperatur unter Rückfluss gerührt. Anschließend wurde die Reaktionsmischung auf Raumtemperatur abgekühlt und filtriert. Nach Entfernen des Lösungsmittels über Rotationsverdampfung wurde das Toluoldiisocyanat-Isomerengemisch erhalten. Der Prozess wurde wiederholt angewandt, um eine ausreichend große Menge Recycling-Toluoldiisocyanat für die Verschäumungsexperimente bereit zu stellen. Formulation 1 prepared. Then 75 g of saturated K 2 CC>3 solution (pKb value 3.67 at 25 °C) were added. The catalyst tetrabutylammonium hydrogen sulfate was then added at 5% by weight, based on the mass of the reaction mixture. The reactor was sealed and the reaction mixture was heated to an internal temperature of 150°C for 14 hours. Upon completion of the 14 hours, heating was discontinued and the reaction mixture was cooled to room temperature. After opening the reactor, the reaction mixture was transferred to a round bottom flask. The water was removed via rotary evaporation and the remaining reaction mixture extracted with cyclohexane and then filtered. The solid which was filtered off was extracted with toluene and the extraction solution obtained was dried. After removing the toluene via rotary evaporation, the toluenediamine was obtained as a mixture of isomers. To convert to the isocyanate, 24 g of the toluenediamine were dissolved in 1.2 L of toluene. Then 250 ml_ of a 0.157 molar solution of triphosgene in toluene were added dropwise. After the addition was complete, the reaction mixture was heated to 110° C. and stirred under reflux at this temperature for 2 h. Then the reaction mixture was cooled to room temperature and filtered. After removing the solvent via rotary evaporation, the toluene diisocyanate isomer mixture was obtained. The process was repeated to provide a large enough amount of recycled toluene diisocyanate for the foaming experiments.
Herstellung von PU-Weichschäumen Production of PU flexible foams
Für die Austestung des recycelten Toluoldiisocyanats hinsichtlich seiner Verschäumungseigenschaften sowie seines Einflusses auf die physikalischen Schaumeigenschaften wurde die folgende Formulierung zur Herstellung von Heißweichschaum verwendet. Hierbei bedeutet beispielsweise 1 ,0 Teil (1 ,0 pphp) einer Komponente 1 g dieser Substanz bezogen auf je 100 g Polyol. The following formulation was used to produce hot flexible foam for testing the recycled toluene diisocyanate with regard to its foaming properties and its influence on the physical foam properties. In this context, for example, 1.0 part (1.0 pphp) of a component means 1 g of this substance per 100 g of polyol.
Tabelle 1 : Formulierung zur Herstellung von PU-Heißweichschäumen. Table 1: Formulation for the production of PU hot-cure flexible foams.
Formulierung 1 Massenteile (pphp) Polyol1» 100 pphp Formulation 1 Parts by mass (pphp) Polyol 1 » 100 pphp
Wasser 4.00 pphp KOSMOS® T92) 0.20 pphp DABCO® DMEA3) 0.15 pphp TEGOSTAB® BF23704» 1.0 pphp Toluoldiisocyanat T 805)variabel, Index von 105 Water 4.00 pphp KOSMOS ® T9 2) 0.20 pphp DABCO ® DMEA 3) 0.15 pphp TEGOSTAB ® BF2370 4 » 1.0 pphp toluene diisocyanate T 80 5) variable, index of 105
1) Polyol: Standard Polyether Polyol Arcol® 1104 erhältlich bei der Firma Covestro, hierbei handelt es sich um ein Glycerin-basiertes Polyetherpolyol mit einer OH-Zahl von 56 mg KOH/g und einer zahlenmittleren Molmasse von 3000 g/mol. 1) Polyol: standard polyether polyol Arcol® 1104 available from Covestro, this is a glycerol-based polyether polyol with an OH number of 56 mg KOH/g and a number-average molar mass of 3000 g/mol.
2) KOSMOS® T9, erhältlich bei der Firma Evonik Industries: Zinn(ll)-Salz der 2-Ethylhexansäure.
3) DABCO® DMEA: Dimethylethanolamin, erhältlich bei der Firma Evonik Industries. Amin- Katalysator zur Herstellung von Polyurethanschäumen 2) KOSMOS® T9, available from Evonik Industries: tin(II) salt of 2-ethylhexanoic acid. 3) DABCO ® DMEA: dimethylethanolamine, available from Evonik Industries. Amine catalyst for the production of polyurethane foams
4) Polyethermodifiziertes Polysiloxan, erhältlich bei der Firma Evonik Industries. 4) Polyether modified polysiloxane available from Evonik Industries.
5) Toluoldiisocyanat: Konventionelles Toluoldiisocyanat Desmodur® T 80 erhältlich bei der Firma Covestro, hierbei handelt es sich um ein Toluoldiisocyanat T 80 (80 % 2,4-lsomer, 20 % 2,6-lsomer) mit einer Viskosität von 3 mPa-s, 48 % NCO und einer Funktionalität von 2 oder erfindungsgemäßes Recycling-Toluoldiisocyanat. 5) Toluene diisocyanate: Desmodur® T 80 conventional toluene diisocyanate, available from Covestro, is a T 80 toluene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) with a viscosity of 3 mPa·s , 48% NCO and a functionality of 2 or recycling toluene diisocyanate according to the invention.
Allgemeine Durchführung zur Herstellung der PU-Heißweichschäume General procedure for the production of PU hot flexible foams
Die Polyurethanschäume wurden als sogenannte Handschäume im Labor hergestellt. Die Herstellung der Schäume erfolgte gemäß folgender Angaben bei 22 °C und 762 mm Hg Luftdruck. Zur Herstellung der Polyurethanschäume nach Formulierung I wurden jeweils 100 g Polyol eingesetzt. Die anderen Formulierungsbestandteile wurden entsprechend umgerechnet. Dabei bedeutete beispielsweise 1 ,0 Teil (1 ,0 pphp) einer Komponente 1 g dieser Substanz je 100 g Polyol. The polyurethane foams were produced in the laboratory as so-called hand foams. The foams were produced according to the following information at 22° C. and 762 mm Hg air pressure. To produce the polyurethane foams according to formulation I, 100 g of polyol were used in each case. The other formulation components were converted accordingly. For example, 1.0 part (1.0 pphp) of a component meant 1 g of this substance per 100 g of polyol.
Für die Schaumstoffe nach Formulierung I wurden in einem Pappbecher der Zinnkatalysator Zinn(ll)- 2-ethylhexanoat, Polyol, das Wasser, die Aminkatalysatoren und der jeweilige Schaumstabilisator vorgelegt und für 60 s mit einem Scheibenrührer bei 1000 U/min vermischt. Nach dem ersten Rühren wurde das Isocyanat zugegeben und mit dem gleichen Rührer für 7 s bei 2500 U/min eingearbeitet und sofort in eine mit Papier ausgekleidete Kiste (19 cm c 19 cm Grundfläche und 19 cm Höhe) überführt. Der Schaum stieg nach dem Eingießen in der Verschäumungsbox auf. Im Idealfall blies der Schaum bei Erreichen der maximalen Steighöhe ab und sackte dann leicht zurück. Dabei öffneten sich die Zellmembranen der Schaumbläschen und eine offenporige Zellstruktur des Schaumstoffs wurde erhalten. For the foams according to formulation I, the tin catalyst tin(II) 2-ethylhexanoate, polyol, the water, the amine catalysts and the respective foam stabilizer were placed in a paper cup and mixed for 60 s with a disc stirrer at 1000 rpm. After the initial stirring, the isocyanate was added and incorporated with the same stirrer for 7 s at 2500 rpm and immediately transferred to a paper-lined box (19 cm x 19 cm base and 19 cm height). After pouring, the foam rose in the foaming box. Ideally, the foam blew off when the maximum rise height was reached and then sagged back slightly. The cell membranes of the foam bubbles opened up and an open-pored cell structure of the foam was obtained.
Zur Beurteilung der Eigenschaften wurden die im folgenden Abschnitt beschriebenen charakteristischen Parameter bestimmt. The characteristic parameters described in the following section were determined to assess the properties.
Anwendungstechnische Tests Application tests
Die hergestellten Schäume wurden anhand folgender physikalischer Eigenschaften bewertet a) Rücksacken des Schaumstoffes nach dem Ende der Steigphase (=Rückfall). The foams produced were evaluated on the basis of the following physical properties: a) Sagging of the foam after the end of the rise phase (=fall back).
Der Rückfall, bzw. das Nachsteigen ergibt sich aus der Differenz der Schaumhöhe nach direktem Abblasen und nach 3 min. nach Abblasen des Schaums. Die Schaumhöhe wird dabei durch eine an einem Zentimetermaß befestigte Nadel auf dem Maximum in der Mitte der Schaumkuppe gemessen. Ein positiver Wert beschreibt hierbei das Rücksacken des Schaumes nach dem Abblasen, ein negativer Wert beschreibt entsprechend das Nachsteigen des Schaumes.
b) Schaumhöhe ist die Höhe des gebildeten, frei gestiegenen Schaums nach 3 Minuten. Die Schaumhöhe wird in Zentimeter (cm) angegeben. c) Steigzeit The relapse or subsequent ascent results from the difference in foam height after direct blowing off and after 3 minutes after blowing off the foam. The foam height is measured using a needle attached to a centimeter ruler at the maximum in the center of the foam dome. A positive value describes the sagging of the foam after blowing off, a negative value describes the subsequent rise of the foam. b) Foam height is the height of the free-rising foam formed after 3 minutes. Foam height is reported in centimeters (cm). c) rise time
Die Zeitspanne zwischen dem Ende des Mischens der Reaktionskomponenten und dem Abblasen des Polyurethanschaums. Die Steigzeit wird in Sekunden (s) angegeben. d) Porosität The time between the end of mixing the reaction components and the blowing off of the polyurethane foam. The rise time is given in seconds (s). d) porosity
Die Luftdurchlässigkeit des Schaums wurde in Anlehnung an DIN EN ISO 4638:1993-07 durch eine Staudruckmessung am Schaumstoff ermittelt. Der gemessene Staudruck wurde in mm Wassersäule angegeben, wobei dann die niedrigeren Staudruckwerte den offeneren Schaum charakterisieren. Die Werte wurden im Bereich von 0 bis 300 mm Wassersäule gemessen. DieThe air permeability of the foam was determined based on DIN EN ISO 4638:1993-07 by measuring the dynamic pressure on the foam. The back pressure measured was given in mm of water column, with the lower back pressure values then characterizing the more open foam. The values were measured in the range from 0 to 300 mm water column. the
Messung des Staudrucks erfolgte mittels einer Apparatur umfassend eine Stickstoffquelle, Reduzierventil mit Manometer, Durchflussregelschraube, Waschflasche, Durchflussmessgerät, T-Stück, Auflagedüse und einem skalierten Glasrohr, in welches Wasser gefüllt ist. Die Auflagedüse weist eine Kantenlänge von 100 x 100 mm, ein Gewicht von 800 g, eine lichte Weite der Austrittsöffnung von 5 mm, eine lichte Weite des unteren Auflageringes von 20 mm und einen Außendurchmesser des unteren Auflageringes von 30 mm auf. The dynamic pressure was measured using an apparatus comprising a nitrogen source, reducing valve with manometer, flow control screw, washing bottle, flow meter, T-piece, support nozzle and a scaled glass tube filled with water. The support nozzle has an edge length of 100×100 mm, a weight of 800 g, a clear width of the outlet opening of 5 mm, a clear width of the lower support ring of 20 mm and an outer diameter of the lower support ring of 30 mm.
Die Messung erfolgt durch Einstellung des Stickstoffvordrucks per Reduzierventil auf 1 bar und Einregeln der Durchflussmenge auf 480 l/h. Die Wassermenge wird im skalierten Glasrohr so eingestellt, dass keine Druckdifferenz aufgebaut und ablesbar ist. Für die Vermessung des Prüfkörpers mit einer Dimension von 150 x 150 x 50 mm wird die Auflagedüse an den Ecken des Prüfkörpers kanten kongruent aufgelegt sowie einmal an der (geschätzten) Mitte des Prüfkörpers (jeweils auf der Seite mit der größten Oberfläche) aufgelegt. Abgelesen wird, wenn sich ein konstanter Staudruck eingestellt hat. Die Auswertung erfolgt durch Mittelwertbildung über die fünf erhaltenen Messwerte. d) Zahl der Zellen pro cm (Zellzahl): Diese wird auf einer Schnittfläche optisch bestimmt (gemessen gemäß DIN EN 15702:2009-04). The measurement is carried out by setting the nitrogen pre-pressure to 1 bar using the reducing valve and adjusting the flow rate to 480 l/h. The amount of water is set in the graduated glass tube in such a way that no pressure difference can be built up and read. For the measurement of the test specimen with dimensions of 150 x 150 x 50 mm, the contact nozzle is placed congruently at the corners of the test specimen edges and once at the (estimated) center of the test specimen (each on the side with the largest surface). It is read when a constant back pressure has been established. The evaluation is carried out by averaging over the five measured values obtained. d) Number of cells per cm (cell number): This is determined optically on a cut surface (measured according to DIN EN 15702:2009-04).
Ergebnisse der Verschäumungen Foaming results
Das erfindungsgemäße Recycling-Toluoldiisocyanat wird in der Formulierung I, Tabelle 1 im Vergleich zum konventionellen Toluoldiisocyanat T 80 ausgeprüft. Die Ergebnisse der anwendungstechnischen Tests für die Verwendung der verschiedenen Isocyanate sind in der Tabelle 2 wiedergegeben.
Tabelle 2: Verschäumungsergebnisse für die PU-Heißweichschäume, hergestellt nach Formulierungl , Tabellel unter Verwendung des erfindungsgemäßen Reycling-Diisocyanats sowie des konventionellen Toluoldiisocyanat Desmodur T 80 der Firma Covestro.
Die Ergebnisse in Tabelle 2 zeigen, dass das erfindungsgemäße Recycling-Toluoldiisocyanat zu 30% als I so cyanatkom ponente eingesetzt werden kann, wobei ein vergleichbares Verschäumungsverhalten analog zu dem bei der Verwendung von 100% des konventionellen Toluoldiisocyanat Desmodur® T 80 beobachtet wird. Insbesondere die Steigzeit bleibt fast unverändert. Die Schaumhöhe von Schaum #2 liegt nur geringfügig unter der von Referenzschaum #1 mit Desmodur® T80. Ebenso weisen die erhalten Schaumkörper #1 und #2 vergleichbare physikalischen Schaumeigenschaften bezüglich Porosität und Zellzahl auf.
The recycling toluene diisocyanate according to the invention is tested in formulation I, Table 1 in comparison with the conventional toluene diisocyanate T 80. Table 2 shows the results of the performance tests for the use of the various isocyanates. Table 2: Foaming results for the hot flexible PU foams, produced according to Formulation 1, Table 1 using the recycling diisocyanate according to the invention and the conventional toluene diisocyanate Desmodur T 80 from Covestro. The results in Table 2 show that the recycling toluene diisocyanate according to the invention can be used at 30% as the isocyanate component, with comparable foaming behavior analogous to that observed when using 100% of the conventional toluene diisocyanate Desmodur® T 80. In particular, the rise time remains almost unchanged. The foam height of foam #2 is only slightly below that of reference foam #1 with Desmodur® T80. Likewise, the foam bodies #1 and #2 obtained have comparable physical foam properties with regard to porosity and cell number.
Claims
1. Verfahren zur Herstellung von aromatischen und/oder aliphatischen Di- und/oder1. Process for the production of aromatic and/or aliphatic di- and/or
Polyisocyanaten, umfassend folgende Schritte a) Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators, welcher aus der Gruppe bestehend aus quartären Ammoniumsalzen enthaltend ein Ammonium Kation umfassend 6 bis 30 Kohlenstoff- Atome und organischen Sulfonaten enthaltend wenigstens 7 Kohlenstoffatome gewählt ist, bei Temperaturen vorzugsweise unter 200 °C unter Erzeugung von Di- und/oder Polyaminen, b) Abtrennung der aus Schritt a) gewonnen Di- und/oder Polyamine von der Reaktionsmischung durch Extraktion, Destillation und/oder anderer Trennverfahren, c) Phosgenierung der aus Schritt b) erhaltenen Di- und/oder Polyamine zu Di- und/oder Polyisocyanaten, wobei in dem Phosgenierungsschritt c) optional auch Di- und/oder Polyamine hinzugefügt werden können, welche nicht aus dem Verfahrensschritt a) stammen. Polyisocyanates comprising the steps of a) depolymerizing a polyurethane by hydrolysis in the presence of a base and a catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation containing 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms Temperatures preferably below 200° C. to produce di- and/or polyamines, b) separating the di- and/or polyamines obtained from step a) from the reaction mixture by extraction, distillation and/or other separation processes, c) phosgenating the from step b) the di- and/or polyamines obtained to form di- and/or polyisocyanates, it being possible in the phosgenation step c) to optionally also add di- and/or polyamines which do not originate from process step a).
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die resultierenden Di- und/oder Polyisocyanate aromatische und/oder aliphatische Di- und/oder Polyisocyanaten umfassen, wie insbesondere Methylendiphenyldiisocyanat, Polymethylen-Polyphenylen- Polyisocyanat, Toluoldiisocyanat und/oder Isophorondiisocyanat, insbesondere Toluoldiisocyanat. 2. The method according to claim 1, characterized in that the resulting di- and / or polyisocyanates include aromatic and / or aliphatic di- and / or polyisocyanates, such as in particular methylene diphenyl diisocyanate, polymethylene polyphenylene polyisocyanate, toluene diisocyanate and / or isophorone diisocyanate, especially toluene diisocyanate .
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Depolymerisation des Polyurethans in Schritt a) unter Einsatz einer Base mit einem pKb Wert bei 25 °C von 1 bis 10, sowie eines Katalysators, der ausgewählt ist aus der Gruppe umfassend quartäre Ammoniumsalze enthaltend ein Ammonium-Kation umfassend 6 bis 30 Kohlenstoff-Atome und organische Sulfonate enthaltend wenigstens 7 Kohlenstoffatome, erfolgt. 3. The method according to claim 1 or 2, characterized in that the depolymerization of the polyurethane in step a) using a base having a pKb value at 25 ° C from 1 to 10, and a catalyst which is selected from the group consisting of quaternary ammonium salts containing an ammonium cation containing from 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms.
4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Depolymerisation des Polyurethans in Schritt a) unter Einsatz einer Base mit einem pKb Wert bei 25 °C von < 1 , sowie eines Katalysators aus der Gruppe der quartären Ammoniumsalze enthaltend ein Ammonium-Kation mit 6 bis 14 Kohlenstoff-Atomen, sofern das Ammonium-Kation keinen Benzylrest umfasst, oder aber enthaltend ein Ammonium-Kation mit 6 bis 12 Kohlenstoff-Atomen, sofern das Ammonium-Kation einen Benzylrest umfasst, erfolgt.
4. The method according to claim 1 or 2, characterized in that the depolymerization of the polyurethane in step a) using a base with a pKb value at 25 ° C of <1, and a catalyst from the group of quaternary ammonium salts containing an ammonium Cation with 6 to 14 carbon atoms if the ammonium cation does not contain a benzyl radical, or containing an ammonium cation with 6 to 12 carbon atoms if the ammonium cation contains a benzyl radical.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das in Schritt a) zu depolymerisierende Polyurethan einen Polyurethanschaum umfasst, vorzugsweise PU-Hartschaum, PU-Weichschaum, PU-Heißweichschaum, viskoelastischer PU-Schaum, HR-PU-Schaum, PU-Hypersoft-Schaum, halbharter PU-Schaum, thermoverformbarer PU- Schaum und/oder PU-lntegralschaum. 5. The method according to any one of claims 1 to 4, characterized in that the polyurethane to be depolymerized in step a) comprises a polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam, viscoelastic PU foam, HR PU foam , PU hypersoft foam, semi-rigid PU foam, thermoformable PU foam and/or PU integral foam.
6. Verwendung eines Di- und/oder Polyisocyanats, erhalten nach einem Verfahren gemäß einem der Ansprüche 1 bis 5 zur Herstellung von Polyurethan, insbesondere PU-Schaum. 6. Use of a di- and/or polyisocyanate obtained by a process as claimed in any of claims 1 to 5 for the production of polyurethane, in particular PU foam.
7. Verfahren zur Herstellung von Polyurethan, insbesondere PU-Schaumstoffen, durch Umsetzung 7. Process for the production of polyurethane, in particular PU foams, by reaction
(a) mindestens einer Polyolkomponente mit (a) at least one polyol component
(b) mindestens einer Isocyanatkomponente in Gegenwart von (b) at least one isocyanate component in the presence of
(c) einem oder mehreren Katalysatoren, die die Reaktionen Isocyanat-Polyol und/oder Isocyanat-Wasser und/oder die Isocyanat-Trimerisierung katalysieren, (c) one or more catalysts which catalyze the isocyanate-polyol and/or isocyanate-water reactions and/or isocyanate trimerization,
(d) zumindest einem Schaumstabilisator sowie (d) at least one foam stabilizer and
(e) optional von ein oder mehreren chemischen oder physikalischen Treibmitteln, dadurch gekennzeichnet, dass die Isocyanatkomponente Recycling-Isocyanat umfasst, erhalten nach einem Verfahren gemäß einem der Ansprüche 1 bis 5 (e) optionally one or more chemical or physical blowing agents, characterized in that the isocyanate component comprises recycled isocyanate obtained by a process according to any one of claims 1 to 5
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass das die Isocyanatkomponente mehr als 30 Gew,-%, vorzugsweise mehr als 50 Gew.-%, bevorzugt mehr als 70 Gew.-%, weiter bevorzugt mehr als 80 Gew.-%, insbesondere mehr als 95 Gew.-% Recycling-Isocyanat enthält, bezogen auf die gesamte Isocyanatkomponente. 8. The method according to claim 7, characterized in that the isocyanate component more than 30% by weight, preferably more than 50% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular contains more than 95% by weight recycled isocyanate, based on the total isocyanate component.
9. Verfahren gemäß Anspruch 7 oder 8, dadurch gekennzeichnet, dass die Polyolkomponente ein Recycling-Polyol umfasst, insbesondere erhalten durch Depolymerisation eines Polyurethans durch Hydrolyse in Gegenwart einer Base und eines Katalysators welcher aus der Gruppe bestehend aus quartären Ammoniumsalzen enthaltend ein Ammonium Kation umfassend 6 bis 30 Kohlenstoff-Atome und organischen Sulfonaten enthaltend wenigstens 7 Kohlenstoffatome gewählt ist. 9. The method according to claim 7 or 8, characterized in that the polyol component comprises a recycling polyol, in particular obtained by depolymerization of a polyurethane by hydrolysis in the presence of a base and a catalyst which from the group consisting of quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms.
10. Verfahren gemäß einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass der Schaumstabilisator ausgewählt ist aus der Gruppe Kohlenstoffatome aufweisenden Siliziumverbindungen, die vorzugsweise durch die Formel (1 c) beschrieben werden, oder Mischungen mehrerer dieser Verbindungen:
Formel (1 c): [R1 2R2SiOi/2]a [R1 3SiOi/2] [R1 2Si022]c [R1R2Si022]d [R3Si03/2]e [Si04/2]f Gg mit a = 0 bis 12, bevorzugt 0 bis 10, besonders bevorzugt 0 bis 8 b = 0 bis 8, bevorzugt 0 bis 6, besonders bevorzugt 0 bis 2 c = 0 bis 250, bevorzugt 1 bis 200, besonders bevorzugt 1 ,5 bis 150 d = 0 bis 40, bevorzugt 0 bis 30, besonders bevorzugt 0 bis 20 e = 0 bis 10, bevorzugt 0 bis 8, besonders bevorzugt 0 bis 6 f = 0 bis 5, bevorzugt 0 bis 3, besonders bevorzugt 0 g = 0 bis 3, bevorzugt 0 bis 2,5, besonders bevorzugt 0 bis 2 wobei: a+b+c+d+e+f+g > 3 a + b > 2 10. The method according to any one of claims 7 to 9, characterized in that the foam stabilizer is selected from the group of silicon compounds containing carbon atoms, which are preferably described by the formula (1c), or mixtures of several of these compounds: Formula (1 c): [R 1 2 R 2 SiOi/ 2 ]a [R 1 3 SiOi/ 2 ] [R 1 2 Si0 22 ] c [R 1 R 2 Si0 22 ] d [R 3 Si0 3/2 ] e [Si0 4/2 ] f G g with a=0 to 12, preferably 0 to 10, particularly preferably 0 to 8 b=0 to 8, preferably 0 to 6, particularly preferably 0 to 2 c=0 to 250, preferably 1 to 200, particularly preferably 1.5 to 150 d=0 to 40, preferably 0 to 30, particularly preferably 0 to 20 e=0 to 10, preferably 0 to 8, particularly preferably 0 to 6 f=0 to 5, preferably 0 to 3, particularly preferably 0 g = 0 to 3, preferably 0 to 2.5, particularly preferably 0 to 2 where: a + b + c + d + e + f + g > 3 a + b > 2
G = unabhängig voneinander die gleichen oder verschiedene Radikale aus (Oi/2)nSiR1m - CH2CHR5 - R4 - CHR5CH2 - SiR1 m(Oi/2)n G = independently the same or different radicals from (Oi/ 2 ) n SiR 1 m - CH 2 CHR 5 - R 4 - CHR 5 CH 2 - SiR 1 m (Oi/ 2 ) n
(Oi/2)nSiR1m - CH2CHR5 - R4 - CR5=CH2 (Oi/2)nSiR1m - CH2CHR5 - R4 - CR5=CR5-CH3 (Oi/ 2 ) n SiR 1 m - CH 2 CHR 5 - R 4 - CR 5 =CH 2 (Oi/ 2 ) n SiR 1 m - CH 2 CHR 5 - R 4 - CR 5 =CR 5 -CH 3
R4 = unabhängig voneinander die gleichen oder verschiedene divalente organische Radikale, bevorzugt zweifache organische Radikale aus 1 bis 50 Kohlenstoffatomen, optional unterbrochen durch Ether-, Ester- oder Amid-Gruppen und optional mit OH-R 4 = independently the same or different divalent organic radicals, preferably double organic radicals of 1 to 50 carbon atoms, optionally interrupted by ether, ester or amide groups and optionally with OH-
Gruppen funktionalisiert, oder (-SiR1 20-)xSiR1 2- Gruppen, besonders bevorzugt die gleichen oder verschiedene divalente organische Radikale aus 2 bis 30 Kohlenstoffatomen, optional unterbrochen durch Ether-, Ester- oder Amid-Gruppen und optional mit OH-Gruppen funktionalisiert, oder (-SiR1 20-)xSiR1 2- Gruppen x = 1 bis 50, bevorzugt 1 bis 25, besonders bevorzugt 1 bis 10 Groups functionalized, or (-SiR 1 2 0-) x SiR 1 2 - groups, particularly preferably the same or different divalent organic radicals of 2 to 30 carbon atoms, optionally interrupted by ether, ester or amide groups and optionally with OH groups functionalized, or (-SiR 1 2 0-) x SiR 1 2 - groups x = 1 to 50, preferably 1 to 25, particularly preferably 1 to 10
R5 = unabhängig voneinander die gleichen oder verschiedene Alkylradikale bestehend aus 1 bis 16 Kohlenstoffatomen, Arylradikale mit 6 bis 16 Kohlenstoffatomen oder Wasserstoff, bevorzugt aus der Gruppe der Alkylradikale mit 1 bis 6 Kohlenstoffatomen oder Arylradikale mit 6 bis 10 Kohlenstoffatomen oder Wasserstoff, besonders bevorzugt Methyl oder Wasserstoff. wobei:
n = 1 oder 2 m = 1 oder 2 n + m = 3 R 5 = independently the same or different alkyl radicals consisting of 1 to 16 carbon atoms, aryl radicals having 6 to 16 carbon atoms or hydrogen, preferably from the group of alkyl radicals having 1 to 6 carbon atoms or aryl radicals having 6 to 10 carbon atoms or hydrogen, particularly preferably methyl or hydrogen. in which: n = 1 or 2 m = 1 or 2 n + m = 3
R1 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 bis 16R 1 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 to 16
Kohlenstoffatomen oder Wasserstoff oder -OR6, bevorzugt Methyl, Ethyl, Octyl, Dodecyl, Phenyl oder Wasserstoff, besonders bevorzugt Methyl oder Phenyl. Carbon atoms or hydrogen or -OR 6 , preferably methyl, ethyl, octyl, dodecyl, phenyl or hydrogen, particularly preferably methyl or phenyl.
R2 = unabhängig voneinander gleiche oder verschiedene Polyether erhältlich durch die Polymerisation von Ethylenoxid und/oder Propylenoxid und/oder anderen Alkylenoxiden wie zum Beispiel Butylenoxid oder Styroloxid mit der generellen Formel (2) oder ein organisches Radikal entsprechend der Formel (3) R 2 = independently identical or different polyethers obtainable by the polymerization of ethylene oxide and/or propylene oxide and/or other alkylene oxides such as butylene oxide or styrene oxide with the general formula (2) or an organic radical corresponding to the formula (3)
(2) - (R7)h - O - [C2H40]i - [CsHeOJj - [CR8 2CR8 20]k - R9 (2) - (R 7 ) h - O - [C 2 H 4 0] i - [CsHeOJj - [CR 8 2 CR 8 2 0] k - R 9
(3) - Oh - R10 wobei h = 0 oder 1 (3) - Oh - R 10 where h = 0 or 1
R7 = divalentes organisches Radikal, bevorzugt divalentes organisches Alkyl- oder Arylradikal optional substituiert mit -OR6, besonders bevorzugt ein divalentes organisches Radikal des Typs CPH2p. i = 0 bis 150, bevorzugt 1 bis 100, besonders bevorzugt 1 bis 80 j = 0 bis 150, bevorzugt 0 bis 100, besonders bevorzugt 0 bis 80 k = 0 bis 80, bevorzugt 0 bis 40, besonders bevorzugt 0 p = 1 - 18, bevorzugt, 1 - 10, besonders bevorzugt 3 oder 4 wobei i + j + k > 3 R3 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale potentiell substituiert mit Heteroatomen, bevorzugt gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16 Kohlenstoffatomen potentiell substituiert mit Halogenatomen, besonders bevorzugt Methyl, Vinyl, Chlorpropyl oder Phenyl. R 7 = divalent organic radical, preferably divalent organic alkyl or aryl radical optionally substituted with -OR 6 , more preferably a divalent organic radical of the type C P H 2p . i = 0 to 150, preferably 1 to 100, particularly preferably 1 to 80 j = 0 to 150, preferably 0 to 100, particularly preferably 0 to 80 k = 0 to 80, preferably 0 to 40, particularly preferably 0 p = 1 - 18, preferably 1-10, particularly preferably 3 or 4 where i + j + k> 3 R 3 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals potentially substituted with heteroatoms, preferably identical or different radicals selected from the Group of saturated or unsaturated alkyl radicals with 1 to 16 carbon atoms or aryl radicals with 6 - 16 carbon atoms potentially substituted with halogen atoms, particularly preferably methyl, vinyl, chloropropyl or phenyl.
R6 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16
Kohlenstoffatome oder Wasserstoff, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 - 8 Kohlenstoffatomen oder Wasserstoff, besonders bevorzugt sind Methyl, Ethyl, Isopropyl oder Wasserstoff. R 6 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals with 1 to 16 carbon atoms or aryl radicals with 6 - 16 Carbon atoms or hydrogen, preferably saturated or unsaturated alkyl radicals having 1-8 carbon atoms or hydrogen, methyl, ethyl, isopropyl or hydrogen being particularly preferred.
R8 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der Alkylradikale mit 1 bis 18 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen und potentiell substituiert mit Heteroatomen wie Halogenatomen, Arylradikale mit 6 - 18 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen, oder Wasserstoff, bevorzugt Alkylradikale mit 1 bis 12 Kohlenstoffatomen potentiell substituiert mit Etherfunktionen und potentiell substituiert mit Heteroatomen wie Halogenatomen oder Arylradikale mit 6 bis 12 Kohlenstoffatomen, potentiell substituiert mit Etherfunktionen, oder Wasserstoff, besonders bevorzugt Methyl, Ethyl, Benzyl oder Wasserstoff. R 8 = identical or different radicals selected from the group of alkyl radicals with 1 to 18 carbon atoms, potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms, aryl radicals with 6 - 18 carbon atoms, potentially substituted with ether functions, or hydrogen, preferably alkyl radicals with 1 to 12 carbon atoms potentially substituted with ether functions and potentially substituted with heteroatoms such as halogen atoms or aryl radicals having 6 to 12 carbon atoms potentially substituted with ether functions, or hydrogen, more preferably methyl, ethyl, benzyl or hydrogen.
R9 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe Wasserstoff, Alkyl, - C(0)-R11, -C(0)0-R11 oder -C(0)NHR11, gesättigt oder ungesättigt, optionaler Weise substituiert mit Heteroatomen, bevorzugt Wasserstoff oder Alkylradikale mit 1 bis 8 Kohlenstoffatomen oder Acetyl-, besonders bevorzugt Wasserstoff, Acetyl, Methyl oder Butyl. R 9 = same or different radicals selected from the group hydrogen, alkyl, -C(0)-R 11 , -C(0)0-R 11 or -C(0)NHR 11 , saturated or unsaturated, optionally substituted with Heteroatoms, preferably hydrogen or alkyl radicals having 1 to 8 carbon atoms or acetyl, particularly preferably hydrogen, acetyl, methyl or butyl.
R10 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der gesättigten oder ungesättigten Alkylradikale oder Arylradikale, potentiell substituiert mit einem oder mehreren OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 bis 18 Kohlenstoffatomen oder Arylradikale mit 6 - 18 Kohlenstoffatomen, optional substituiert mit einem oder mehreren OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten, besonders bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 bis 18 Kohlenstoffatomen oder Arylradikale mit 6 - 18 Kohlenstoffatomen substituiert mit mindestens einem OH, Ether, Epoxid, Ester, Amin und/oder Halogen-Substitutenten. R 10 = identical or different radicals selected from the group of saturated or unsaturated alkyl radicals or aryl radicals, potentially substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, preferably saturated or unsaturated alkyl radicals with 1 to 18 Carbon atoms or aryl radicals with 6-18 carbon atoms optionally substituted with one or more OH, ether, epoxide, ester, amine and/or halogen substituents, more preferably saturated or unsaturated alkyl radicals with 1-18 carbon atoms or aryl radicals with 6-18 carbon atoms with at least one OH, ether, epoxide, ester, amine and/or halogen substituent.
R11 = gleiche oder verschiedene Radikale ausgewählt aus der Gruppe der Alkylradikale mit 1 bis 16 Kohlenstoffatomen oder Arylradikale mit 6 - 16 Kohlenstoffatomen, bevorzugt gesättigte oder ungesättigte Alkylradikale mit 1 - 8 Kohlenstoffatomen oder Arylradikale mit 6 - 12 Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, Butyl oder Phenyl. R 11 = identical or different radicals selected from the group of alkyl radicals having 1 to 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms, preferably saturated or unsaturated alkyl radicals having 1 - 8 carbon atoms or aryl radicals having 6 - 12 carbon atoms, particularly preferably methyl, ethyl, butyl or phenyl.
11. Verfahren nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass der Katalysator zur Herstellung von PU-Schaum ausgewählt ist aus Triethylendiamin, 1 ,4- diazabicyclo[2.2.2]octan-2-methanol, Diethanolamin, N-[2-[2-(Dimethylamino)ethoxy]ethyl]- N-methyl-1 ,3-propandiamin, 2-[[2-(2-(Dimethylamino)ethoxy)ethyl]methylamino]ethanol,11. The method according to any one of claims 7 to 10, characterized in that the catalyst for the production of PU foam is selected from triethylenediamine, 1, 4-diazabicyclo [2.2.2] octane-2-methanol, diethanolamine, N- [2 -[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, 2-[[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol,
1 ,1'-[(3-{bis[3-(dimethylamino)propyl]-amino}propyl)imino]dipropan-2-ol, [3- (Dimethylamino)propyl]harnstoff, 1 ,3-Bis[3-(dimethylamino)propyl]harnstoff und/oder Aminkatalysatoren der allgemeinen Struktur (1 a) und/oder der Struktur (1 b):
1,1'-[(3-{bis[3-(dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, [3-(dimethylamino)propyl]urea, 1,3-bis[3- (dimethylamino)propyl]urea and/or amine catalysts of general structure (1a) and/or structure (1b):
X umfasst Sauerstoff, Stickstoff, Hydroxyl, Amine der Struktur (NR111 oder NRmRlv) oder Harnstoffgruppen (N(RV)C(0)N(RVI) oder N(RV")C(0)NRVIRV") Y umfasst Amine NRVIIIRIX oder Ether ORlx X includes oxygen, nitrogen, hydroxyl, amines of structure (NR 111 or NR m R lv ) or urea groups (N(R V )C(O)N(R VI ) or N(R V ")C(O)NR VI R V ") Y includes amines NR VIII R IX or ethers OR lx
RUI umfassen gleiche oder verschiedene lineare oder cyclische, aliphatische oder aromatische Kohlenwasserstoffe mit 1-8 Kohlenstoffatomen die ggf. mit einer OH Gruppe funktionalisiert sind; und/oder umfassen Wasserstoff R UI include identical or different linear or cyclic, aliphatic or aromatic hydrocarbons with 1-8 carbon atoms which are optionally functionalized with an OH group; and/or comprise hydrogen
RIII IX umfassen gleiche oder verschiedene lineare oder cyclische, aliphatische oder aromatische Kohlenwasserstoffe mit 1-8 Kohlenstoffatomen die ggf. mit einer OH Gruppe, einer NH oder einer NH2 Gruppe funktionalisiert sind; und/oder umfassen Wasserstoff m = 0 bis 4, bevorzugt 2 oder 3 n = 2 bis 6, bevorzugt 2 oder 3 i = 0 bis 3, bevorzugt 0-2
R III IX include identical or different linear or cyclic, aliphatic or aromatic hydrocarbons with 1-8 carbon atoms which are optionally functionalized with an OH group, an NH or an NH2 group; and/or comprise hydrogen m = 0 to 4, preferably 2 or 3 n = 2 to 6, preferably 2 or 3 i = 0 to 3, preferably 0-2
Z N - R x
ZN-Rx
(lb) (lbs)
Rx umfasst gleiche oder verschiedene Reste bestehend aus Wasserstoff und/oder lineare, verzweigte oder cyclische aliphatische oder aromatische Kohlenwasserstoffe mit 1 - 18 Kohlenstoffatomen, die mit 0 - 1 Hydroxylgruppen und 0 - 1 NH2-Gruppen substituiert sein können.R x includes identical or different radicals consisting of hydrogen and/or linear, branched or cyclic aliphatic or aromatic hydrocarbons with 1-18 carbon atoms, which can be substituted with 0-1 hydroxyl groups and 0-1 NH 2 groups.
Z umfasst Sauerstoff, N-Rx oder CH2. und/oder Z includes oxygen, NRx or CH2. and or
Metallverbindungen einschließlich organometallischer Metallsalze, organischer Metallsalze, anorganischer Metallsalze sowie organometallischer Verbindungen der Metalle Sn, Bi, Zn, AI oder K, vorzugsweise Sn oder Bi, oder deren Mischungen.
Metal compounds including organometallic metal salts, organic metal salts, inorganic metal salts and organometallic compounds of the metals Sn, Bi, Zn, Al or K, preferably Sn or Bi, or mixtures thereof.
12. Zusammensetzung, geeignet zur Herstellung von Polyurethan-Schaum, umfassend mindestens eine Polyolkomponente, mindestens eine Isocyanatkomponente, Katalysator, Schaumstabilisator, Treibmittel sowie optionale Hilfsmittel, dadurch gekennzeichnet, dass die Isocyanatkomponente Recycling-Isocyanat umfasst, erhalten nach einem Verfahren gemäß einem der Ansprüche 1 bis 512. Composition suitable for producing polyurethane foam, comprising at least one polyol component, at least one isocyanate component, catalyst, foam stabilizer, blowing agent and optional auxiliaries, characterized in that the isocyanate component comprises recycled isocyanate obtained by a process according to any one of claims 1 until 5
13. Polyurethanschaum, vorzugsweise PU-Hartschaum, PU-Weichschaum, PU-Heißweichschaum, viskoelastischer PU-Schaum, HR-PU-Schaum, PU-Hypersoft-Schaum, halbharter PU-Schaum, thermoverformbarer PU-Schaum oder PU-lntegralschaum, bevorzugt PU-Heißweichschaum, HR- PU-Schaum, PU-Hypersoft-Schaum oder viskoelastischer PU-Schaum, am meisten bevorzugt PU- Heißweichschaum dadurch gekennzeichnet, dass er durch ein Verfahren gemäß einem der Ansprüche 7 bis 10 erhalten wird. 13. Polyurethane foam, preferably PU rigid foam, PU flexible foam, PU hot flexible foam, viscoelastic PU foam, HR PU foam, PU hypersoft foam, semi-rigid PU foam, thermoformable PU foam or PU integral foam, preferably PU -Hot flexible foam, HR PU foam, PU hypersoft foam or viscoelastic PU foam, most preferably PU hot flexible foam, characterized in that it is obtained by a process according to any one of claims 7 to 10.
14. Verwendung von PU-Schäumen gemäß Anspruch 13 als Kühlschrankisolierung, Dämmplatte, Sandwichelement, Rohrisolation, Sprühschaum, 1- & 1 ,5-Komponenten-Dosenschaum, Holzimitat, Modellschaum, Verpackungsschaum, Matratze, Möbelpolster, Automobil-Sitzpolster, Kopfstütze, Instrumententafel, Automobil-Innenverkleidung, Automobil-Dachhimmel, Schallabsorptionsmaterial, Lenkrad, Schuhsole, Teppichrückseitenschaum, Filterschaum, Dichtschaum, Dichtmittel und Kleber, Beschichtung oder zur Herstellung entsprechender Produkte.
14. Use of PU foams according to claim 13 as refrigerator insulation, insulating board, sandwich element, pipe insulation, spray foam, 1- & 1.5-component canned foam, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automobile seat upholstery, headrest, instrument panel, Automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant and adhesive, coating or to make related products.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP21183452 | 2021-07-02 | ||
PCT/EP2022/067705 WO2023275036A1 (en) | 2021-07-02 | 2022-06-28 | Recovering di- and/or polyisocyanates from pu-depolymerisation processes |
Publications (1)
Publication Number | Publication Date |
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EP4363479A1 true EP4363479A1 (en) | 2024-05-08 |
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ID=76764918
Family Applications (1)
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EP22738453.4A Pending EP4363479A1 (en) | 2021-07-02 | 2022-06-28 | Recovering di- and/or polyisocyanates from pu-depolymerisation processes |
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Country | Link |
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US (1) | US20240294724A1 (en) |
EP (1) | EP4363479A1 (en) |
CN (1) | CN117642446A (en) |
CA (1) | CA3223887A1 (en) |
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WO2023208946A1 (en) | 2022-04-27 | 2023-11-02 | Covestro Deutschland Ag | Method for recovering raw materials from isocyanurate-containing polyurethane products |
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- 2022-06-28 MX MX2023014999A patent/MX2023014999A/en unknown
- 2022-06-28 CN CN202280047219.XA patent/CN117642446A/en active Pending
- 2022-06-28 WO PCT/EP2022/067705 patent/WO2023275036A1/en active Application Filing
- 2022-06-28 US US18/575,871 patent/US20240294724A1/en active Pending
- 2022-06-28 CA CA3223887A patent/CA3223887A1/en active Pending
- 2022-06-28 EP EP22738453.4A patent/EP4363479A1/en active Pending
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