GB1596420A - Rapidly crystallising polyester compositions - Google Patents
Rapidly crystallising polyester compositions Download PDFInfo
- Publication number
- GB1596420A GB1596420A GB5430/78A GB543078A GB1596420A GB 1596420 A GB1596420 A GB 1596420A GB 5430/78 A GB5430/78 A GB 5430/78A GB 543078 A GB543078 A GB 543078A GB 1596420 A GB1596420 A GB 1596420A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- phthalic acid
- composition
- acid ester
- atoms
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims description 32
- 229920000728 polyester Polymers 0.000 title description 10
- -1 phthalic acid ester Chemical class 0.000 claims description 40
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 21
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-M terephthalate(1-) Chemical compound OC(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-M 0.000 claims description 4
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 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
- 239000003054 catalyst Substances 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006085 branching agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NQEUTICDPLLXAY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxycarbonyl]benzoic acid Chemical compound OCCOCCOCCOC(=O)C1=CC=CC=C1C(O)=O NQEUTICDPLLXAY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- RHIAOOMCMLDTKE-UHFFFAOYSA-L butanedioate;cadmium(2+) Chemical class [Cd+2].[O-]C(=O)CCC([O-])=O RHIAOOMCMLDTKE-UHFFFAOYSA-L 0.000 description 2
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JCMLRUNDSXARRW-UHFFFAOYSA-N trioxouranium Chemical compound O=[U](=O)=O JCMLRUNDSXARRW-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- APTGHASZJUAUCP-UHFFFAOYSA-N 1-n,4-n-di(octan-2-yl)benzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(NC(C)CCCCCC)C=C1 APTGHASZJUAUCP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- IUYYVMKHUXDWEU-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,1-diol Chemical compound CC(C)CC(C)(C)C(O)O IUYYVMKHUXDWEU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 1
- BXJCEULFBLJODE-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphite Chemical compound OP(O)OCCCl BXJCEULFBLJODE-UHFFFAOYSA-N 0.000 description 1
- ACOQOLIJGGKILA-UHFFFAOYSA-N 2-methylpentane-1,1-diol Chemical compound CCCC(C)C(O)O ACOQOLIJGGKILA-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Substances Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- UCXOJWUKTTTYFB-UHFFFAOYSA-N antimony;heptahydrate Chemical compound O.O.O.O.O.O.O.[Sb].[Sb] UCXOJWUKTTTYFB-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- NINLDBMTAAKRTR-UHFFFAOYSA-L barium(2+);propanedioate Chemical compound [Ba+2].[O-]C(=O)CC([O-])=O NINLDBMTAAKRTR-UHFFFAOYSA-L 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- RZRVLCQUJJCGDC-UHFFFAOYSA-N dodecyl phenyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OC1=CC=CC=C1 RZRVLCQUJJCGDC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- IJHFIVUWUURYJD-UHFFFAOYSA-M lanthanum(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[La+3] IJHFIVUWUURYJD-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical class [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- LVZZABGEQTZXHP-UHFFFAOYSA-L strontium;propanedioate Chemical class [Sr+2].[O-]C(=O)CC([O-])=O LVZZABGEQTZXHP-UHFFFAOYSA-L 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
(54) RAPIDLY CRYSTALLISING POLYESTER
COMPOSITIONS
(71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of the Federal Republic of Germany, of 509 Leverkusen, Germany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to highly crystalline, rapidly crystallizing thermoplastic compositions comprising a high molecular weight polyalkylene terephthalate and a phthalic acid ester.
Polyalkylene terephthalates are used for manufacturing fibres, films and moulded articles. They have excellent physical properties such as high wear resistance, durability, and high dimensional accuracy, i.e. due to their partly crystalline structure and they are, therefore, particularly suitable for the manufacture of heavy duty moulded articles. The mechanical properties can be further improved by incorporating reinforcing materials such as glass-fibres (British Patent No. 1,111,012, US-Patent No. 3,368,995, and German
Auslegeschrift No. 2,042,447).
Polyethylene terephthalate (PET) is particularly suitable for the manufacture of fibres, filaments, and sheets, but it is hardly suitable for injection moulding because of high moulding temperatures (approximately 1400C) and relatively long moulding times required. These stringent processing conditions prevent the use of polyethylene terephthalate for injection moulding in spite of its high rigidity and heat distortion temperature.
Although polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) require shorter moulding times and lower moulding temperatures (approximately 80"C) owing to their higher rate of crystallisation, they are inferior to polyethylene terephthalate in their physical properties, particularly in their heat distortion temperature.
High crystallinity ensures hardness, dimensional stability and resistance to distortion even at elevated temperatures. For optimum properties high crystallinity must be arrived at as rapidly as possible. Thus, in polyethylene terephthalate crystallisatioff can be improved and accelerated by nucleation with finely divided inorganic solids (Netherlands Patent Application No. 65.11744). The injection moulding cycle time which governs the economics of the process depends on the time interval for which the cast must stay in the mould. These cycles are too long even at high moulding temperature and, therefore, prevent the wide use of polyethylene terephthaate in the manufacture of injection moulded articles.
Developing of other polyalkylene terephthalates which have a higher crystallisation velocity and higher crystallinity is, therefore, necessary. We have sought to provide polyalkylene terephthalates which contain from 0.5 to 30% by weight of a phthalic acid ester. Such mixtures have improved crystallisation velocity.
In these polyester compositions the degree of crystallinity required for high dimensional stability is achieved more rapidly so that the injection moulding cycles are substantially shortened. Also, the moulding temperature can be lower without impairing the crystallisation behaviour. The injection moulded casts, therefore, cool more rapidly, and the residence time in the mould is, therefore, also reduced.
The present invention provides a highly crystalline, rapidly crystallising thermoplastic composition comprising
(1) from 70 to 99.5% by weight of a high molecular weight polyalkylene terephthalate having an intrinsic viscosity of at least 0.6 dl/g (determined on a 0.5 O by weight solution in a mixture of phenol and tetrachloroethane in proportions by weight of 1:1 at 250C), and
(2) from 0.5 to 30% by weight of a phthalic acid ester having an average molecular weight of from 200 to 2000, represented by the following formula::
wherein Rl represents a branched chain aliphatic group having from 3 to 12 C-atoms,
R2 and R3 each independently represents a linear or branched chain aliphatic group having from 1 to 12 C-atoms,
n represents 0 or an integer of from 1 to 4, and
x represents 0 or an integer of from 1 to 15, with the proviso that, when the phthalic acid ester is di-2-ethylhexyl phthalate, the proportion of the phthalic acid ester is not substantially 0.5% by weight, and with the further proviso that the composition does not contain a polyolefin or vinyl type polymer when component (2) is dibutyl phthalate or dioctyl phthalate.
The composition preferably comprises from 8599.5% by weight of the polyalkylene terephthalate and from 0.515% by weight of the phthalic acid ester.
The intrinsic viscosity of the polyalkylene terephthalate is preferably at least 0.8 dl/g.
The average molecular weight of the phthalic acid ester (2), even if it is a mixture of oligomers, can be determined by vapour pressure osmosis in acetone.
The present invention also provides a process for the production of highly crystalline, rapidly crystallising thermoplastic compositions, wherein from 70 to 99.5% by weight, preferably from 85 to 99.5% by weight, of a high molecular weight polyalkylene terephthalate having an intrinsic viscosity of at least 0.6 dl/g, preferably at least 0.8 dl/g (determined on an 0.5% by weight solution in a mixture of phenol and tetrachloroethane in proportions by weight of 1:1 at 250C) and from 0.5 to 30% by weight, preferably from 0.5 to 15% by weight, of a phthalic acid ester of formula I above are mixed together and homogenised in the melt. The operation can be carried out in a mixing screw extruder, for example; the solidified melt can, subsequently, be granulated.
The dicarboxylic acid component of the polyalkylene terephthalate (1) consists of terephthalic acid which may contain up to 10 mol%, based on the acid component of other aromatic dicarboxylic acids having from 6 to 14 C-atoms, of aliphatic dicarboxylic acids having from 4 to 8 C-atoms, or of cycloaliphatic dicarboxylic acids having from 8 to 12 C-atoms. Examples of such dicarboxylic acids are phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, adipic acid, sebacic acid, and cyclohexanediacetic acid.
The diol component of the polyalkylene terephthalate is, for example, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol or cyclohexane-l,4-dimethanol and, preferably, ethylene glycol; it may contain up to 10 mol% of other aliphatic diols having from 3 to 8 C-atoms, cycloaliphatic diols having from 6 to 15 C-atoms or aromatic diols having from 6 to 21 C-atoms.
Examples of such additional diols ("Codiols") include 3 - methylpentanediol (2,4), 2 - methylpentanediol - (1,4), 2,2,4 - trimethylpentanediol - (1,3), 2ethylhexanediol - (1,3), 2,2 - diethylpropanediol - (1,3), hexanediol - (1,3), 1,4 di - (,B - hydroxyethoxy) - benzene, 2,2 - bis - (4 - hydroxycyclohexyl) - propane, 2,4 - dihydroxy - 1,1,3,3 - tetramethyl - cyclobutane, 2,2 - bis - (3 - '3 p hydroxyethoxyphenyl) - propane and 2,2 - bis - (4 - hydroxypropoxyphenyl) propane.
The polyalkylene terephthalates (1) can be branched by incorporating trihydric or tetrahydric alcohols or tribasic or tetrabasic acids as described in
German Offenlegungsschrift No. 1,900,270 and in US Patent No. 3,692,744.
Examples of suitable branching agents include trimesic acid, pyromellitic acid, trimethylolpropane and ethane, and pentaerythritol. It is advisable not to use more than 1 mol% of branching agent, based on the quantity of acid component.
The polyalkylene terephthalates can be prepared in known manner by
a) esterification or transesterification of terephthalic acid and/or of the corresponding dialkylterephthalates, preferably the dimethyl ester, with from 1.05 to 5.0 mol, preferably from 1.4 to 3.6 mol of the diol, based on 1 mol of the dicarboxylic acid component, and optionally the branching agent, in the presence of esterification and/or transesterification catalysts (first stage), and
b) polycondensation of the resulting reaction products in the presence of polycondensation catalysts at temperatures between 200 and 320"C at reduced pressure (preferably below 1 Torr) (second stage).
Both the first step (a) and the second step (b) of condensation are usually carried out in the presence of catalysts, e.g., those described by R. E. Wilfong in J.
Polym. Sci. 54, 385 (1961). Some of these catalysts (A) are more powerful accelerators of the esterification reaction, (a) others (B) for the polycondensation reaction (b), still others (C) are fairly active for both (a) and (b).
The following are examples: catalysts (A) which are suitable for accelerating reaction (a):
1. Lithium, sodium, potassium, calcium, strontium and boron in the form of the metals or their oxides, hydrides, formates, acetates, alcoholates or glycollates; 2. Calcium and strontium chlorides and bromides;
3. tertiary amines;
4. Calcium and strontium malonates, adipates, benzoates, etc.;
5. Lithium salts of dithiocarbamic acids.
The following are examples of catalysts (B) suitable for the polycondensation reaction (b):
1. Molybdenum, germanium, lead, tin, and antimony in the form of the metals or their oxides, hydrides, formates, alcoholates or glycollates;
2. Zinc and lead perborates and borates;
3. Zinc, manganese(II), cobalt, magnesium, chromium, iron and cadmium succinates, butyrates, adipates or enolates of a diketone;
4. Zinc chloride and bromide;
5. Lanthanum dioxide and titanate;
6. Neodymium chloride;
7. Mixed salts of antimony, e.g. potassium antimony tartrate, and salts of antimonic acids, such as potassium pyroantimonate; 8. Zinc or manganese salts of dithiocarbamic acids;
9. Cobalt naphthenate; 10. Titanium tetrafluoride or tetrachloride; Il. Alkyl ortho-titanates;
12.Titanium tetrachloride ether complexes;
13. Quaternary ammonium salts carrying a titanium hexaalkoxy group; titanium tetraalkoxides, alkali metal or alkaline earth metal compounds of aluminium, zirconium or titanium alkoxides;
14. Organic quaternary ammonium, sulphonium, phosphonium and oxonium hydroxides and salts;
15. Barium malonate, adipate, benzoate, etc;
16. Lead, zinc, cadmium or manganese salts of the monoalkyl ester of a phenylene dicarboxylic acid;
17. Antimony catechuic complexes with an amino alcohol or with an amine and an alcohol;
18. Uranium trioxide, tetrahalide, nitrate, sulphate or acetate.
The following are examples of catalysts (C) which are suitable for accelerating both steps (a) & (b) of the reaction;
1. Barium, magnesium, zinc, cadmium, aluminium, manganese and cobalt as the metals or their oxides, hydrides, formates, alcoholates, glycolates or, preferably, as acetates;
2. Aluminium chloride and bromide;
3. Zinc, manganese(II), cobalt, magnesium, chromium, iron and cadmium succinates, butyrates, adipates or enolates of a diketone.
The most suitable compounds for use as catalysts (A) are calcium, zinc and manganese salts, particularly the acetates.
The most suitable catalysts (B) are the compounds of zinc, manganese, cobalt, antimony, germanium, titanium and tin, e.g. zinc and manganese acetate, antimony trioxide, trichloride and triacetate, and germanium dioxide and tetrachloride.
The most suitable catalysts (C) are particularly the titanium compounds, e.g.
tetraalkyltitanium acid esters having alkyl groups with from 1 to 10 C-atoms, such as tetraisopropyltitanate and tetrabutyltitanate.
The catalysts are used in quantities of from 0.001 to 0.2% by weight, based on the dicarboxylic acid components.
Inhibitors may be added in the process to inhibit the catalysts (A) after completion of the first reaction step (a) and to increase the stability of the end product.
(cf. "Polyesterfasern" by H. Ludewig, 2nd Edition, publishers Akademie
Verlag, Berlin 1974). The following are examples of such inhibitors: phosphoric acid, phosphorous acid and aliphatic, aromatic and araliphatic esters thereof, e.g.
the alkyl esters having from 6 to 18 C-atoms in the alochol component, phenyl esters in which the phenyl groups can carry 1 to 3 substituents having 6 to 18 Catoms, such as trinonylphenyl phosphate, dodecyl phenyl phosphate or triphenyl phosphate. These inhibitors are usually added in quantities of from 0.01 to 0.6? by weight, based on the dicarboxylic acid component.
In order to obtain an even higher molecular weight, the polyalkylene terephthalates may be subjected to a solid phase polycondensation. This is generally carried out by subjecting the granulated product to a temperature which is from 60 to 60C below the melting point of the polymer, either in a steam of nitrogen or under a vacuum of less than 1 Torr.
The phthalic acid esters (2) can be prepared by esterification or transesterification of phthalic acid, its anhydride and/or its dialkyl esters, preferably its methyl esters, with monohydric alcohols or with monohydric and dihydric alcohols. A detailed description of the various methods of preparation is in
E. Miller, "Methoden der Organischen Chemie" (Houben-Weyl), Vol. 14/2, page 1 et seq., Georg Thieme Verlag, Stuttgart 1963, and in V. V. Korshak and S. V.
Vinogradova, "Polyesters", Pergamon Press, Oxford 1965, pages 34-63.
The following are examples of suitable phthalic acid- esters (2):
diisopropylphthalate.
ditert.-butylphthalate,
di-2-ethylhexylphthalate,
diisononylphthalate, and
di-isononyl-poly-triethylene glycol phthalate.
The mixtures of polyalkylene terephthalate (1) and phthalic acid ester (2) can be obtained in usual commercial mixing apparatus such as kneaders and one-shaft or two-shaft screw-extruders. The solidified melt of the mixtures can be granulated for further processing, and this can be followed by a post-condensation in the solid phase.
The usual quantities of stabilizers, preferably from 0.01 to 0.5o by wt. based on the weight of the polyalkylene terephthalates (exclusive fillers or reinforcements) can be added to protect against thermooxidative degradation.
Suitable stabilizers include phenols and phenol derivatives, particularly sterically hindered phenols which have alkyl substituents with 1 to 6 C-atoms in both orthopositions to the phenolic hydroxyl group, amines, preferably secondary arylamines and their derivatives, phosphates and phosphites, preferably their aryl derivatives, quinones, copper salts of organic acids, addition compounds of copper (1) halides with phosphites, e.g. 4,4' - bis - (2,6 - di - tert. - butylphenol); 1,3,5 - trimethyl 2,4,6 - tris - (3,5 - di - tert. - butyl- 4 - hydroxy - benzyl) - benzene; 4,4' butylidene - bis - (6 - tert. - butyl - m - cresol); 3,5 - di - tert. - butyl - 4 hydroxy - benzyl - phosphonic acid diethyl ester; N,N' - bis - (p - naphthyl) - p phenylenediamine; N,N' - bis - (1 - methylheptyl) - p - phenylenediamine; phenyl -'3 - naphthylamine; 4,4' - bis - (,cr - dimethylbenzyl) - diphenylamine; 1,3,5 - tris - (3,5 - di - tert. - butyl - 4 - hydroxy - hydrocinnamoyl)hexahydro - S - triazine; hydroquinone; p - benzoquinone; toluhydroquinone; p tert.-butyl-pyrocatechol; chloranil; naphthoquinone; copper naphthenate; copper octoate; Cu(I)Cl/triphenylphosphate; Cu(I)Cl/trimethylphosphite; Cu(I)Cl/tris chloroethylphosphite; Cu(I)Cl/tripropylphosphite; and p-nitrosodimethylaniline.
The thermoplastic compositions of the invention can be reinforced, e.g., with metals, silicates, carbon and glass, primarily, in the form of fibres and woven or non-woven webs. Glass fibres are preferred.
Inorganic or organic pigments, dyes, lubricants and mould release agents such as zinc stearate, montan wax, and UV absorbers can also be added in the usual quantities.
Flame-retardant compositions are obtained by the addition of from 2 to 20% by weight, based on the composition of known flame-retarding agents such as halogen-containing compounds, elementary phosphorus or phosphorus compounds, phosphorus-nitrogen compounds, antimony trioxide or mixtures of these, preferably antimony trioxide, decarbromobiphenyl ether and tetrabromobisphenol-A-polycarbonate.
The crystallisation velocity of the thermoplastic polyester moulding compositions can be further increased by adding nucleating agents in quantities of from 0.01 to 1% by weight, based on the quantity of polyester without filler or reinforcing material. Compounds of this kind are known in the art (cf. Kunststoff
Handbuch, Volume VIII, "Polyester", Carl Hanser Verlag, Munich, 1973, page 701).
The thermoplastic compositions of this invention are suitable for the manufacture of all kinds of moulded articles by injection moulding.
Examples
An injection mould designed for the production of a gear wheel (diameter 40 mm) was used for determining the length of processing cycle required. The moulded product was ejected from the mould by four ejector pins. The minimum injection cycle at which the ejector pins just failed to penetrate the moulded product and the product dropped from the mould without difficulty was determined.
Table 1 shows the length of time required in the mould as well as the total length of the injection moulding cycle of some polyester compositions according to the invention based on polyethylene terephthalate (intrinsic viscosity 0.94 dl/g) and phthalic acid esters (Examples 1 and 2), compared with the corresponding times required for unmodified polyethylene terephthalate. The comparison Examples 34 show the behaviour under processing conditions of polyethylene terephthalate mixtures containing phthalic acid esters which have linear aliphatic alcohols as end groups. Although these polyester compositions can be extruded to fully crystalline products at a lower mould temperature than pure polyethylene terephthalate, the residence time in the mould and the length of the whole operating cycle cannot be shortened.
TABLE 1
Phthalic acid ester Temperature Tenperature Residence time Total injection
Quantity of cylinder of mould in mould moulding cycle
Example Name (% by wt.) ( C) ( C) (sec.) (sec.) 1 Di-isononyl- 5 260 107 17.5 19.5 phthalate 2 Di-isononyl- 5 260 110 14.5 16.5 poly-triethyleneglycolphthalate* 3 Di-ethyl- 5 260 111 47.5 49.5 phthalate 4 Di-n-butyl- 5 260 112 42.5 44.5 phthalate 5 - - 270 140 37.5 39.5 *Average molecular weight about 700.
TABLE 2
Response under conditions of processing of polyester compositions based on copolyethylene terephthalate (0.6 mol% of 2-ethylhexanediol-(1,3)) and phthalic acid esters
Phthalic acid ester Temperature Temperature Residence time Total injection
Quantity of cylinder of mould in mould moulding cycle
Example Name (% by wt.) ( C) ( C) (sec.) (sec.) 1 di-isononyl- 5 260 110 12.5 14.5 phthalate 2 Di-isononyl 5 260 108 10.5 12.5 poly-triethylene glycol phthalate 3 - - 270 130 17.5 19.5
Claims (8)
1. A highly crystalline, rapidly crystallising thermoplastic composition comprising
(1) from 70 to 99.5% by weight of a high molecular weight polyalkylene terephthalate having an intrinsic viscosity of at least 0.6 dl/g (determined on a 0.5% by weight solution in a mixture of phenol and tetrachloroethane in proportions by weight of 1:1 at 250C), and
(2) from 0.5 to 30% by weight of a phthalic acid ester having an average molecular weight of from 200 to 2000, represented by the following formula::
wherein
R' represents a branched chain aliphatic group having from 3 to 12 C-atoms,
R2 and R3 each independently represents a linear or branched chain aliphatic group having from 1 to 12 C-atoms,
n represents 0 or an integer of from 1 to 4, and
x represents 0 or an integer of from 1 to 15, with the proviso that, when the phthalic acid ester is di-2-ethylhexyl phthalate, the proportion of the phthalic acid ester is not substantially 0.5% by weight, and with the further proviso that the composition does not contain a polyolefin or vinyl type polymer when component (2) is dibutyl phthalate or dioctyl phthalate.
2. A composition as claimed in Claim 1, comprising from 85 to 99.5% by weight of the polyalkylene terephthalate (1) and from 0.5 to 15% by weight of the phthalic acid ester (2).
3. A composition as claimed in Claim 1, substantially as hereinbefore described with reference to Example 1 or 2.
4. A process for the preparation of a composition according to Claim 1, which comprises mixing together and homogenising in the melt from 70 to 99.5% by weight of a high molecular weight polyalkylene terephthalate (1) as defined in
Claim I and from 0.5 to 30% by weight of a phthalic acid ester (2) as defined in
Claim 1.
5. A process as claimed in Claim 4, substantially as hereinbefore described with reference to Example 1 or 2.
6. A composition prepared by a process as claimed in Claim 4 or 5.
7. An injection moulding process wherein a composition as claimed in any one of Claims 1 to 3 and 6 is used.
8. Moulded products prepared by a process as claimed in Claim 7.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2706128A DE2706128C2 (en) | 1977-02-14 | 1977-02-14 | Rapidly crystallizing polyester compositions and process for their production |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1596420A true GB1596420A (en) | 1981-08-26 |
Family
ID=6001116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB5430/78A Expired GB1596420A (en) | 1977-02-14 | 1978-02-10 | Rapidly crystallising polyester compositions |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPS53101046A (en) |
DE (1) | DE2706128C2 (en) |
FR (1) | FR2380324A1 (en) |
GB (1) | GB1596420A (en) |
IT (1) | IT1101777B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4352904A (en) | 1978-02-28 | 1982-10-05 | E. I. Du Pont De Nemours And Company | Molding resins |
USRE32334E (en) * | 1978-02-28 | 1987-01-20 | E. I. Du Pont De Nemours And Company | Molding resins |
DE3066225D1 (en) * | 1979-02-23 | 1984-03-01 | Rohm & Haas | Polyester compositions and processes for moulding them |
DE3066633D1 (en) * | 1979-11-19 | 1984-03-22 | Bayer Ag | Use of polyethylene terephthalate moulding masses containing an organic imide in the preparation of crystalline mouldings by injection moulding at low mould temperatures |
US4351757A (en) * | 1980-10-24 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Molding material of polyethylene terephthalate and alkai metal salt of C30 -C54 substantially aliphatic carboxylic acid |
US4620026A (en) * | 1984-08-10 | 1986-10-28 | The Dow Chemical Company | Monomeric plasticizers for halogen-containing resins |
US4539356A (en) * | 1984-10-17 | 1985-09-03 | Gaf Corporation | Polyethylene terephthalate molding composition |
US5047450A (en) * | 1988-04-05 | 1991-09-10 | Phillips Petroleum Company | Polyethylene terephthalate molding resin blends |
DE4007882C2 (en) * | 1990-03-13 | 1994-03-10 | Boehringer Ingelheim Kg | Use of polyglycolic acid and its derivatives as nucleating agents |
DE19930705A1 (en) | 1999-07-02 | 2001-01-04 | Buna Sow Leuna Olefinverb Gmbh | Process for the preparation of polyethylene terephthalate modified with o-phthalic acid units |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6608999A (en) * | 1965-11-20 | 1967-02-27 | ||
US3516957A (en) * | 1968-04-29 | 1970-06-23 | Eastman Kodak Co | Thermoplastic polyester composition containing organic ester mold release agent |
DE2124336C3 (en) * | 1971-05-17 | 1986-07-31 | Hoechst Ag, 6230 Frankfurt | Thermoplastic polyester molding compounds |
-
1977
- 1977-02-14 DE DE2706128A patent/DE2706128C2/en not_active Expired
-
1978
- 1978-02-10 GB GB5430/78A patent/GB1596420A/en not_active Expired
- 1978-02-10 IT IT48002/78A patent/IT1101777B/en active
- 1978-02-13 JP JP1420578A patent/JPS53101046A/en active Pending
- 1978-02-14 FR FR7804154A patent/FR2380324A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
DE2706128A1 (en) | 1978-08-17 |
DE2706128C2 (en) | 1986-12-11 |
IT1101777B (en) | 1985-10-07 |
IT7848002A0 (en) | 1978-02-10 |
JPS53101046A (en) | 1978-09-04 |
FR2380324B1 (en) | 1983-06-03 |
FR2380324A1 (en) | 1978-09-08 |
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PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |