CN111909039A - Preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect - Google Patents
Preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect Download PDFInfo
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- CN111909039A CN111909039A CN202010925968.0A CN202010925968A CN111909039A CN 111909039 A CN111909039 A CN 111909039A CN 202010925968 A CN202010925968 A CN 202010925968A CN 111909039 A CN111909039 A CN 111909039A
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- Prior art keywords
- ketone
- steric hindrance
- diamine
- aliphatic
- high steric
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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 46
- 230000000694 effects Effects 0.000 title claims abstract description 31
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 150000002576 ketones Chemical class 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- -1 diketone imine Chemical class 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 239000013067 intermediate product Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 150000004985 diamines Chemical group 0.000 claims description 22
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 claims description 20
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 8
- MKLARKDYEBNZFK-UHFFFAOYSA-N 2,5-dimethylcyclopentan-1-one Chemical compound CC1CCC(C)C1=O MKLARKDYEBNZFK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- HFNWDYQEGABWQS-UHFFFAOYSA-N 2,6-dimethylheptan-3-one Chemical compound CC(C)CCC(=O)C(C)C HFNWDYQEGABWQS-UHFFFAOYSA-N 0.000 claims description 6
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 claims description 6
- VZXXYILNWWRSGE-UHFFFAOYSA-N 3,5-dimethylheptan-4-one Chemical compound CCC(C)C(=O)C(C)CC VZXXYILNWWRSGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 5
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- JWTVQZQPKHXGFM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diamine Chemical compound CC(C)(N)CCC(C)(C)N JWTVQZQPKHXGFM-UHFFFAOYSA-N 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 22
- 239000004970 Chain extender Substances 0.000 abstract description 21
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003822 epoxy resin Substances 0.000 abstract description 13
- 229920000647 polyepoxide Polymers 0.000 abstract description 13
- 229920002396 Polyurea Polymers 0.000 abstract description 10
- 229920003226 polyurethane urea Polymers 0.000 abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 5
- 125000000547 substituted alkyl group Chemical group 0.000 abstract description 5
- 125000004427 diamine group Chemical group 0.000 abstract description 3
- 150000003335 secondary amines Chemical class 0.000 description 28
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 25
- 238000005984 hydrogenation reaction Methods 0.000 description 22
- 239000004814 polyurethane Substances 0.000 description 16
- 239000006227 byproduct Substances 0.000 description 14
- 150000004658 ketimines Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000004705 aldimines Chemical class 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229940009098 aspartate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000162 poly(ureaurethane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of aliphatic secondary diamine with high steric hindrance effect comprises the steps of taking aliphatic primary diamine and ketone as raw materials, adopting a catalyst, reducing intermediate product (namely, diketone imine) of the aliphatic primary diamine and the ketone into a secondary diamine product with high steric hindrance alkyl as a substituent of each secondary amino group under the hydrogen atmosphere at the temperature of 40-160 ℃ and the reaction pressure of 0.5-8 Mpa. The aliphatic series dibasic secondary amine with high steric hindrance effect synthesized by the invention has lower reaction activity due to the steric hindrance effect of the substituted alkyl on the N atom, and can be used as a slow chain extender or curing agent of polyurea, polyurethane urea and epoxy resin.
Description
Technical Field
The invention belongs to the technical field of special chemicals and fine chemical engineering, and relates to a preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect.
Background
The application range of polyurethane/polyurea and epoxy resin is wide, one curing agent cannot meet all requirements, and the development of chain extenders with various varieties and multiple performances is particularly important.
The diamine compound is a chain extender or a curing agent of polyurethane (polyurea) elastomer and epoxy resin materials, and can also be used for synthesizing polyamide. In the field of non-foamed polyurethane mainly comprising elastic polyurethane materials (including cast polyurethane elastomers, plastic polyurethane paving materials, polyurethane waterproof coatings, adhesives, sealants, pouring sealants, polyurethane urea spraying and polyurea spraying, and reaction injection molding polyurethane materials), diamine is an important auxiliary agent, wherein aromatic diamine is the most commonly used, such as 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 3, 5-diethyltoluenediamine (DETDDA, trade name Ethacure 100 or E-100), 3, 5-dimethylthiotoluenediamine (DMTDA, E-300) and the like, and the diamine chain extender is characterized by containing rigid benzene rings and can endow products with higher strength. MOCA is the most well known solid diamine curing agent in the field of polyurethane elastomers, requires heating when used, and cannot be used directly in room temperature curing systems. The liquid chain extenders DETDA and DMTDA are also widely applied to polyurethane/polyurea, although the liquid auxiliaries are convenient to use, the liquid auxiliaries have high reactivity and are not suitable for manual pouring or construction occasions, particularly the DETDA has high reactivity and needs to be mixed with other chain extenders for use. In addition, a common disadvantage of the aromatic diamine chain extenders is that the color tends to deepen under the irradiation of ultraviolet rays, which is not the case if a sufficient amount of an ultraviolet absorber or light stabilizer is added for outdoor products, while the aliphatic curing agent is used. The common micromolecule aliphatic straight-chain diamine has high primary amine group activity, too fast reaction with isocyanate and short gel time, so that the operation is extremely difficult, and therefore, the diamine is rarely used as a chain extender and a curing agent of isocyanate prepolymer, and only ethylenediamine and isophorone diamine can be used as a rear chain extender of aliphatic waterborne polyurethane.
The liquid resin of the fast curing system may have problems of poor adhesion and detachment of the coating or the glue from the substrate due to short time and poor wettability to the substrate. Slow curing systems are also being appreciated.
Secondary amino [ -NHR (R') ] is less reactive than primary amino due to steric hindrance of the alkyl group substituted on its N atom, and thus secondary amines are less reactive than primary amines and can be used as slow chain extenders or curing agents for polyureas, polyurethanes, and epoxy resins. When the aliphatic dibasic secondary amine is used as the curing agent of the two-component polyurethane/polyurea, the operable time of the polyurethane/polyurea system can be prolonged compared with the commonly used aromatic dibasic primary amine, the prepared two-component polyurethane has more proper in-kettle service life, and the wetting and adhering performance of the polyurea or polyurethane urea coating to a substrate is improved. Particularly, certain high-steric-hindrance secondary diamines containing large substituents have proper reactivity, and the large substituted alkyl can be used as an internal plasticizer to endow cured products with good flexibility. The binary secondary amine chain extender can be compounded with high-activity aromatic binary primary amine and the like for use, and the proper gel time-curing time balance can be obtained by adjusting the proportion of the binary secondary amine chain extender and the high-activity aromatic binary primary amine, so that the balance of the operation performance and the mechanical performance is obtained.
The secondary diamine has the other advantages of low viscosity, no need of melting in use and convenient operation.
The polyurethane material fields such as manually poured polyurethane elastomers, adhesives, sealants, pouring sealants, coatings and the like and the epoxy resin have stronger requirements on low-reactivity secondary amine chain extenders. A common aromatic bis-amino chain extender/curing agent is liquid 4,4 '-bis-sec-butylaminodiphenylmethane (Unilink 4200, Wanalink 6200), an amino group of which is located on a benzene ring, and a hydrogen atom on a nitrogen atom is substituted by isobutyl, so that the activity of the chain extender/curing agent is much lower than that of a substituted precursor, namely 4,4' -diaminodiphenylmethane (MDA), and the chain extender/curing agent is widely applied to the fields of polyurethane adhesives, sealants and the like. In addition, the aspartate resin is also a raw material containing secondary amino groups, and can be used for preparing a bi-component polyaspartate polyurea coating with mild curing speed.
When the diamine is used as a curing agent for epoxy resin, not only the curing time of epoxy resin can be prolonged and the workability can be improved, but also the physical properties such as flexibility of a cured product can be improved as compared with primary diamine. This is because (1) secondary amino groups have one less active hydrogen atom than primary amino groups, the degree of crosslinking is reduced; (2) the secondary diamine has a larger molecular weight than the primary diamine precursor, and the substituent group has an internal plasticizer effect. In addition, primary amine curing agents commonly used for epoxy resin coatings are liable to react with carbon dioxide in the air, resulting in defects such as cloudiness and spots on the coating surface, and secondary amine curing agents can improve this problem. Secondary amine generated by alkyl substitution of primary amino is more hydrophobic than original primary amine, so that the phenomenon of fogging is reduced, the volatility is also reduced, and the pungent smell is obviously weakened. Therefore, the secondary diamine also has a good application market in the field of epoxy resin.
The aliphatic secondary amine chain extender has very few varieties in the market, so the invention provides a production method of aliphatic secondary diamine with high steric hindrance.
There are various methods for producing secondary amino group-containing compounds, for example, a primary amino group-and secondary amino group-containing compound can be obtained from a nitrile compound by high-pressure high-temperature hydrogenation, and a secondary amino group compound can also be obtained from an aldimine and a ketimine having a C = N double bond by hydrogenation reduction; the Michael addition also produces products having secondary amino groups, but with too long a reaction time.
For example, U.S. Pat. No. 4, 4126640A (General Mills Chemicals) earlier reported that aldehydes or ketones were reacted with primary amino groups on polyamines such as diethylenetriamine in benzene-based solvents, water as a by-product was removed by azeotropic distillation, and the solvent was distilled off to give ketimines or aldimine intermediates, which were then reduced by pressure hydrogenation in the presence of Raney nickel catalyst at 145 ℃ to give low viscosity secondary amino group-containing polyamines, which can be used as curing agents for epoxy resins. Chinese patents CN103261145 and CN103261145 (SIKA technology, switzerland) describe methods of reacting polyamine with aldehyde compound to obtain aldimine, and then performing hydrogenation reaction to synthesize aliphatic polybasic secondary amine containing 2 or more secondary amino groups. The method adopts a two-step method to prepare the secondary polyamine, wherein the first step is that the amine reacts with ketone/aldehyde to obtain an intermediate product of ketimine or aldimine, and then fractional distillation and purification are carried out; the second step is the hydrogenation reduction of ketimine/aldimine to give a final product which is a mixture containing secondary amino/imino groups. The secondary polyamine curing agent prepared by the method disclosed in the patent can be used for curing epoxy resin with low requirement on the purity, but when the secondary polyamine curing agent is used as a polyurethane (urea) curing agent and a chain extender, the application is limited because the purity of the curing agent is not high or the functionality is too high. Further, there are reports of a method for producing a non-aliphatic amine compound having a secondary amino group, for example, chinese patent CN109535412A (shanghai donghai university chemical limited) describes a method for producing a secondary amino silane coupling agent by a michael addition reaction of a terminal allyl polyether and a terminal primary amino silane coupling agent. Chinese patent CN105860053A (Nanjing university of forestry) discloses a production method for continuously preparing low-molecular-weight terminal secondary amino polyether by using polyether polyol, hydrogen and liquid ammonia as raw materials and a self-made Ni/Cu/Ti catalyst under the conditions of 180-260 ℃ and 0.5-8 MPa of pressure and adopting a fixed bed method, wherein when the method is adopted, the reaction temperature is high.
Disclosure of Invention
The invention aims to provide a preparation method of aliphatic dibasic secondary amine with high steric hindrance effect.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a preparation method of aliphatic secondary diamine with high steric hindrance effect comprises the steps of taking aliphatic primary diamine and ketone as raw materials, adopting a catalyst, reducing intermediate product (namely, diketone imine) of the aliphatic primary diamine and the ketone into a secondary diamine product with high steric hindrance alkyl as a substituent of each secondary amino group under the hydrogen atmosphere at the temperature of 40-160 ℃ and the reaction pressure of 0.5-8 Mpa, wherein the structural formula is as follows:
wherein R represents a linear or branched alkylene group having no cyclic structure, and the number of carbon atoms in the alkylene group is 2 to 10; r1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms, and R1And R2The total carbon number of (1) is 3-12.
The preferable technical scheme is as follows: the aliphatic dibasic primary amine is at least one of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 2, 5-dimethylhexane-2, 5-diamine, 1, 9-nonanediamine and 1, 10-decanediamine.
The preferable technical scheme is as follows: the ketone is at least one of methyl ethyl ketone, methyl isobutyl ketone, pinacolone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, isophorone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone, and 2, 5-dimethylcyclopentanone.
The preferable technical scheme is as follows: the ketone is at least one of methyl isobutyl ketone, pinacolone, methyl isoamyl ketone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone and 2, 5-dimethylcyclopentanone.
The preferable technical scheme is as follows: the molar ratio of the ketone to the aliphatic diamine primary amine is 2.5-10: 1.
the preferable technical scheme is as follows: the catalyst is selected from rhodium, ruthenium, palladium, platinum or Raney nickel loaded on activated carbon; or rhodium, ruthenium, palladium, platinum, or raney nickel supported on silica; or from rhodium, ruthenium, palladium, platinum, or raney nickel supported on alumina; the dosage of the catalyst is 0.05-10% of the mass of the alicyclic diprimary amine.
The preferable technical scheme is as follows: the temperature is 50-120 ℃, and the reaction pressure is 1.5-6 MPa.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
the aliphatic diamine with high steric hindrance effect synthesized by the invention has lower reaction activity due to the steric hindrance effect of the substituted alkyl on the N atom, can be used as a slow chain extender or curing agent of polyurea, polyurethane urea and epoxy resin, is used for adjusting the operation time, curing speed and flexibility of a two-component polyurethane and epoxy resin system, and has good yellowing resistance compared with a common aromatic diamine chain extender/curing agent.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
The invention aims to provide an environment-friendly preparation method of aliphatic secondary diamine with a linear chain/branched chain structure, which has the advantages of high product yield, high purity, convenient operation, no toxicity, no pollution and low reactivity. The target product can give good flexibility to the product while obviously reducing the reactivity.
The secondary amine has 2 substituted alkyl groups on the alpha-carbon of the amino, namely, the substituent group on the N atom belongs to secondary carbon substituted alkyl groups, so that the steric effect is obvious, and the reactivity of the secondary amino is effectively reduced. And can impart good flexibility to the article. However, the synthesis of aliphatic dibasic secondary amine with amino containing large alkyl substituent has certain difficulty.
The structural formula of the aliphatic dibasic secondary amine synthesized by the invention is as follows:
r is a linear or branched alkylene group having no cyclic structure and having 2 to 10 carbon atoms. Two substituents R of CH in position alpha to a secondary amino group1And R2Each is an alkyl group, each has 1 to 6 carbon atoms, and R1、R2The total carbon number of (2) is 4 to 12, preferably 4 to 8, and one of them is preferably a branched alkyl group.
The invention is technically characterized in that the aliphatic dibasic secondary amine with the structural formula is synthesized by taking diketiminate as an intermediate to carry out hydrogenation reduction reaction, and the main raw materials of the ketimine are aliphatic dibasic primary amine and ketone.
The method adopts ketone as one of raw materials, and the hydrogenation product secondary amine of the ketimine generated by the reaction of the ketone and the amine has larger steric effect compared with the hydrogenation product secondary amine of the aldimine generated by the reaction of the aldehyde and the amine; and one side of the ketone carbonyl group is preferably provided with an alkyl branched chain, so that the steric hindrance of the target product of the secondary amino group participating in the reaction is increased, and the reaction activity of the secondary amine chain extender/curing agent can be obviously reduced.
The higher ketones (higher ketones) include methyl ethyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone (pinacolone), methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, isophorone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone, 2, 5-dimethylcyclopentanone, and the like, and ketones having a large number of carbon atoms and containing a pendant group, such as pinacolone, methyl isoamyl ketone, diisobutyl ketone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone, and 2, 5-dimethylcyclopentanone, are preferable. Methyl tert-butyl ketone was specifically chosen in this example.
The invention adopts straight chain or branched chain aliphatic dibasic primary amine as one of the raw materials, and can preferably select the aliphatic dibasic primary amine with symmetrical molecular structure, so that 2 secondary amino groups of the product have the same or similar reaction activity. The aliphatic dibasic primary amines which may be used include ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 3-pentylenediamine, 2-methylpentylenediamine, 1, 6-hexylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 2,4, 4-trimethylhexane-1, 6-diamine, 1, 9-nonylenediamine, 1, 10-decyldiamine and the like, and preferably aliphatic dibasic primary amines whose molecular structures are substantially symmetrical, such as ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine. This example specifically selects 1, 7-heptanediamine.
The reaction for synthesizing secondary amine by using primary amine and ketone as main raw materials can be carried out in two steps, namely, in the first step, ketimine is synthesized by dehydration, and in the second step, ketimine is reduced into secondary amine by hydrogenation; or adopting a one-step method, namely directly hydrogenating the intermediate reaction product of the ketone and the primary amine without processing to obtain the target product.
The method adopts a one-step method to prepare secondary amine, and comprises the steps of putting a mixture of primary diamine and ketone and a hydrogenation catalyst into a high-pressure reaction kettle, heating, and carrying out hydrogenation and pressurization reduction reaction to obtain the final target product secondary diamine. The step of separating and purifying the ketimine intermediate product is omitted in the synthesis process, water is not removed in the reaction process, benzene or toluene solvent is not used, the whole synthesis process is simple and environment-friendly, and compared with a two-step method, the yield is not obviously influenced by the one-step method.
The invention designs the ketone excess, the molar ratio of the ketone to the aliphatic diamine primary amine is (2.5-10): 1, and preferably (2.5-6): 1. The appropriate excess of ketone is beneficial to improving the conversion rate of the primary diamine, and the excess ketone can be recycled as a solvent. The specific molar ratio of the embodiment is 8: 1
The hydrogenation catalyst used in the present invention is a catalyst supported on a metal such as platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), or nickel (Ni), and preferably a catalyst supported on carbon such as platinum or palladium. This example specifically selects platinum on carbon.
For example, the Pd/C catalysts include D3H1 (Pd content 3%) and D3H5A (Pd content 3%) of Shaanxi Rui materials GmbH and P1145 (Pd content 5%) of Wingchun, and the Pt/C catalysts preferably include T3H1X-2 (Pt content 3%) of Shaanxi Rui materials GmbH and P2065 (Pt content 3%) of Wingchun. The hydrogenation catalyst is selective for different feedstocks and the hydrogenation catalyst used in the present invention is not limited to these exemplified species.
The dosage of the catalyst is 0.05-10 percent, preferably 0.3-6 percent based on the aliphatic diamine. This example specifically selects 4%.
The hydrogen gas is industrial high-purity hydrogen.
The reaction vessel adopted by the process is a pressure-resistant stainless steel reaction kettle which meets the supervision requirements of special equipment, and is provided with a stirrer, a thermometer, a reflux condenser and the like, and a fractionating tower is adopted for separating products.
Since the highly sterically hindered organics react more slowly than the less sterically hindered ones, the synthesis time is in the range of 40 hours. The hydrogenation reaction temperature is 40-160 ℃, and preferably 50-120 ℃. This example is specifically 80 ℃.
The preparation reaction process of the invention comprises two steps, primary amine and ketone firstly react to generate ketimine and water, and the over-stoichiometric addition of the raw material ketone can dilute the water generated in the reaction process and reduce the influence of water on the equilibrium reaction; also, the carbon-nitrogen double bond hydrogenation reaction proceeds simultaneously with the ketimine formation reaction, and consumption of ketimine accelerates the ketimine formation reaction to the right. Along with the reaction, the reaction temperature and the hydrogen pressure can be properly increased, so that the incompletely reacted intermediate in the reaction process is promoted to move to the right. The reaction pressure is 0.5-8 MPa, and the preferable pressure is 1.0-5.5 MPa. This example is specifically 3 MPa
And after the hydrogenation secondary amination reaction is finished, carrying out post-treatment on a secondary diamine crude product, filtering to remove the catalyst, distilling, separating excessive ketone, by-product alcohol generated by reduction hydrogenation of the ketone and a small amount of single side hydrogenation by-products which are not completely reacted, and finally obtaining a target product with the purity of over 98.5%.
The alcohol by-product can be converted to a ketone by a process such as sulfuric acid dehydration, or can be used as a solvent.
The excess unreacted ketone obtained by fractional distillation can be recycled after recovery. A small amount of monoimino and single secondary amino hydrogenation byproducts belong to incomplete reaction products, have asymmetric group structures and can be called as single-side byproducts, and the single-side byproducts can be used as raw materials after being fractionated and recovered, and are doped in a small amount for use in the next feeding process. The intermediate product and the product content can be determined by a gas chromatography or the like. The hydrogenation catalyst can be reused after being filtered or the noble metal can be recovered. In conclusion, the method disclosed by the invention is simple in process, green and environment-friendly and has little influence on the environment.
Example 2: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
Adding 88.2 g (1.0 mol) of 1, 4-butanediamine, 426.7g (3.0 mol) of diisobutyl ketone and 0.9 g of platinum-carbon catalyst into a stainless steel high-pressure reaction vessel, closing a feeding port, replacing air in the reaction vessel with nitrogen for 3 times, replacing the nitrogen with hydrogen for 3 times, starting to heat, controlling the temperature to be 60 ℃ and the hydrogen pressure to be not higher than 6.0 MPa, reacting for 10 hours under the condition, gradually raising the temperature, controlling the highest reaction temperature to be within 92 ℃, cooling to 28 ℃ after the total reaction is carried out for 25 hours, discharging the hydrogen, replacing residual hydrogen with the nitrogen, and recovering to normal pressure. And filtering the reaction product, and recycling the filter residue which is used as the catalyst. The filtrate was distilled under reduced pressure using a water ring vacuum pump, and excess ketone, by-product water and by-product alcohol were first distilled off at a lower temperature. Then switching to a rotary vane vacuum pump to remove unilateral by-products. Then continuously raising the temperature or improving the vacuum degree, and distilling the target product N, N' -bis (2, 6-dimethyl-4-heptyl) -1, 4-butanediamine.
After the reaction is finished, the content of the components is measured by gas chromatography: the conversion rate of butanediamine is close to 100 percent, the yield of N, N' -di (2, 6-dimethyl-4-heptyl) -1, 4-butanediamine calculated by butanediamine is 72.6 percent, and the purity can reach 99.5 percent.
Example 3: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
102.8g (1.0 mol) of 1, 5-pentanediamine, 274.1g (2.4 mol) of 2, 4-dimethyl-3-pentanone, and 5g of palladium on carbon catalyst were put into a stainless steel high-pressure reactor, and the atmosphere in the reactor was replaced with nitrogen gas 3 times. And replacing nitrogen with hydrogen for 3 times, heating, controlling the pressure of the hydrogen to be 3.0-3.5 MPa, controlling the initial temperature of the reaction to be 60 ℃, gradually raising the temperature along with the reaction, controlling the highest reaction temperature to be within 95 ℃, after the hydrogenation reaction is carried out for 20 hours, cooling, emptying hydrogen, replacing residual hydrogen with the nitrogen, and restoring to the normal pressure. And filtering the reaction product, and recycling the filter residue which is used as the catalyst. Excess 2, 4-dimethyl-3-pentanone, byproduct water and 2, 4-dimethyl-3-pentanol are distilled out under reduced pressure, then a single side byproduct is removed by increasing the temperature, and after the byproduct is removed, the temperature is continuously increased or the vacuum degree is increased, and the target product N, N' -di (2, 4-dimethyl-3-pentyl) -1, 5-pentanediamine is distilled out. After the reaction is finished, the content of the components is measured by gas chromatography: the conversion rate of the 1, 5-pentanediamine is nearly 100 percent, the yield of the N, N' -di (2, 4-dimethyl-3-amyl) -1, 5-pentanediamine is 75.8 percent based on the pentanediamine, and the purity can reach 99.2 percent.
Example 4: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
The procedure of example 2 was repeated by charging 102.8g (1.0 mol) of 1, 5-pentanediamine, 571 g (5.0 mol) of 2, 4-dimethyl-3-pentanone (containing 40% of recovered and distilled 2, 4-dimethyl-3-pentanone), 25g of recovered unreacted unilateral by-product and 6g of filtered and recovered Pt/C catalyst into a high-pressure reactor, and the conversion of 1, 5-pentanediamine was close to 100% as measured by gas chromatography after the reaction was completed. The desired product, N' -bis (2, 4-dimethyl-3-pentyl) -1, 5-pentanediamine, was obtained in an amount of 253.5g and a purity of 98.6%. After the catalyst is repeatedly used for 2 times, the catalytic activity is not obviously reduced.
Example 5: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
A preparation method of aliphatic secondary diamine with high steric hindrance effect takes aliphatic primary diamine and ketone as raw materials, adopts a catalyst, reduces intermediate product diketone imine of the aliphatic primary diamine and the ketone into secondary diamine product with high steric hindrance alkyl as a substituent of each secondary amino group at the temperature of 90 ℃ and the reaction pressure of 7 Mpa under hydrogen atmosphere, and has the following structural formula:
in the formula, R represents alkylene of 2-methyl pentanediamine after two H groups are removed; r1Represents methyl, R2Represents an isobutyl group.
The preferred embodiment is: the molar ratio of ketone to aliphatic diamine primary amine is 2.5: 1.
the preferred embodiment is: the catalyst is selected from rhodium supported on activated carbon; the dosage of the catalyst is 0.05 percent of the mass of the alicyclic diprimary amine.
The preferred embodiment is: the temperature was 50 ℃ and the reaction pressure was 1.5 MPa.
Example 6: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
A preparation method of aliphatic secondary diamine with high steric hindrance effect takes aliphatic primary diamine and ketone as raw materials, adopts a catalyst, reduces intermediate product diketone imine of the aliphatic primary diamine and the ketone into secondary diamine product with high steric hindrance alkyl as a substituent of each secondary amino group under the hydrogen atmosphere at the temperature of 160 ℃ and the reaction pressure of 8Mpa, and has the following structural formula:
wherein R represents a linear or branched alkylene group having no cyclic structure, and the number of carbon atoms in the alkylene group is 2 to 10; r1And R2Independently of each otherAn alkyl group having 1 to 6 carbon atoms and R1And R2The total carbon number of (1) is 3-12.
The preferred embodiment is: the aliphatic diamine is ethylenediamine.
The preferred embodiment is: the ketone is pinacolone.
The preferred embodiment is: the molar ratio of ketone to aliphatic diamine primary amine is 10: 1.
the preferred embodiment is: the catalyst is rhodium supported on silica.
The preferred embodiment is: the temperature is 120 ℃ and the reaction pressure is 6 MPa.
Example 7: preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect
A preparation method of aliphatic secondary diamine with high steric hindrance effect takes aliphatic primary diamine and ketone as raw materials, adopts a catalyst, reduces intermediate product diketone imine of the aliphatic primary diamine and the ketone into secondary diamine product with high steric hindrance alkyl as a substituent of each secondary amino group at the temperature of 50 ℃ and the reaction pressure of 1 Mpa under hydrogen atmosphere, and has the following structural formula:
wherein R represents a linear or branched alkylene group having no cyclic structure, and the number of carbon atoms in the alkylene group is 2 to 10; r1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms, and R1And R2The total carbon number of (1) is 3-12.
The preferred embodiment is: the aliphatic dibasic primary amine is 2, 5-dimethyl hexane-2, 5 diamine.
The preferred embodiment is: the ketone is 2, 5-dimethylcyclopentanone.
The preferred embodiment is: the molar ratio of ketone to aliphatic diamine primary amine is 3: 1.
the preferred embodiment is: platinum on alumina supported by the catalyst; the dosage of the catalyst is 0.1 percent of the mass of the alicyclic diprimary amine.
The preferred embodiment is: the temperature is 60 ℃ and the reaction pressure is 2 MPa.
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, and any modifications or variations thereof that fall within the spirit of the invention are intended to be included within the scope thereof.
Claims (7)
1. A preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect is characterized in that: aliphatic diamine primary amine and ketone are used as raw materials, a catalyst is adopted, the temperature is 40-160 ℃, the reaction pressure is 0.5-8 Mpa, and the intermediate product of the aliphatic diamine primary amine and the ketone, namely the diketone imine, is reduced into a secondary diamine product with one substituent of each secondary amino group as a high steric hindered alkyl group in a hydrogen atmosphere, wherein the structural formula is as follows:
wherein R represents a linear or branched alkylene group having no cyclic structure, and the number of carbon atoms in the alkylene group is 2 to 10; r1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms, and R1And R2The total carbon number of (1) is 3-12.
2. The method for preparing secondary aliphatic diamines with high steric hindrance according to claim 1, wherein: the aliphatic dibasic primary amine is at least one of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 2, 5-dimethylhexane-2, 5-diamine, 1, 9-nonanediamine and 1, 10-decanediamine.
3. The method for preparing secondary aliphatic diamines with high steric hindrance according to claim 1, wherein: the ketone is at least one of methyl ethyl ketone, methyl isobutyl ketone, pinacolone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, isophorone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone, and 2, 5-dimethylcyclopentanone.
4. The method for preparing secondary aliphatic diamine with high steric hindrance according to claim 3, wherein: the ketone is at least one of methyl isobutyl ketone, pinacolone, methyl isoamyl ketone, 2, 4-dimethyl-3-pentanone, 2, 6-dimethyl-3-heptanone, 3, 5-dimethyl-4-heptanone, 2-methylcyclohexanone and 2, 5-dimethylcyclopentanone.
5. The method for preparing secondary aliphatic diamines with high steric hindrance according to claim 1, wherein: the molar ratio of the ketone to the aliphatic diamine primary amine is 2.5-10: 1.
6. the method for preparing secondary aliphatic diamines with high steric hindrance according to claim 1, wherein: the catalyst is selected from rhodium, ruthenium, palladium, platinum or Raney nickel loaded on activated carbon; or rhodium, ruthenium, palladium, platinum, or raney nickel supported on silica; or from rhodium, ruthenium, palladium, platinum, or raney nickel supported on alumina; the dosage of the catalyst is 0.05-10% of the mass of the alicyclic diprimary amine.
7. The method for preparing secondary aliphatic diamines with high steric hindrance according to claim 1, wherein: the temperature is 50-120 ℃, and the reaction pressure is 1.5-6 MPa.
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| CN114315607A (en) * | 2021-12-29 | 2022-04-12 | 万华化学集团股份有限公司 | Preparation method of secondary diamine |
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| CN114773593A (en) * | 2021-05-11 | 2022-07-22 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of secondary amine polyurea resin with large steric hindrance |
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| CN114773593A (en) * | 2021-05-11 | 2022-07-22 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of secondary amine polyurea resin with large steric hindrance |
| CN114773593B (en) * | 2021-05-11 | 2024-04-05 | 深圳飞扬骏研新材料股份有限公司 | Synthesis method and application of large-steric-hindrance secondary amine polyurea resin |
| CN114044869A (en) * | 2021-12-02 | 2022-02-15 | 万华化学集团股份有限公司 | Secondary amine chain-extending cross-linking agent and polyurethane elastic material |
| CN114410271A (en) * | 2021-12-21 | 2022-04-29 | 日丰企业集团有限公司 | Two-component polyurethane seam beautifying agent and preparation method and application thereof |
| CN114410271B (en) * | 2021-12-21 | 2023-11-03 | 日丰企业集团有限公司 | Double-component polyurethane joint beautifying agent and preparation method and application thereof |
| CN114315607A (en) * | 2021-12-29 | 2022-04-12 | 万华化学集团股份有限公司 | Preparation method of secondary diamine |
| CN114315607B (en) * | 2021-12-29 | 2024-02-02 | 万华化学集团股份有限公司 | Preparation method of secondary diamine |
| CN115974699A (en) * | 2022-12-25 | 2023-04-18 | 江苏湘园化工有限公司 | Preparation method of aromatic diamine |
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