TWI588176B - 聚酯樹脂組成物及其製備方法 - Google Patents
聚酯樹脂組成物及其製備方法 Download PDFInfo
- Publication number
- TWI588176B TWI588176B TW101103077A TW101103077A TWI588176B TW I588176 B TWI588176 B TW I588176B TW 101103077 A TW101103077 A TW 101103077A TW 101103077 A TW101103077 A TW 101103077A TW I588176 B TWI588176 B TW I588176B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyester resin
- copolymerized polyester
- dicarboxylic acid
- resin composition
- antioxidant
- Prior art date
Links
- 239000004645 polyester resin Substances 0.000 title claims description 124
- 229920001225 polyester resin Polymers 0.000 title claims description 124
- 239000000203 mixture Substances 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 62
- 230000003078 antioxidant effect Effects 0.000 claims description 56
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 51
- 150000002009 diols Chemical class 0.000 claims description 43
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 27
- 229960002479 isosorbide Drugs 0.000 claims description 26
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 150000003568 thioethers Chemical class 0.000 claims description 9
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 235000013361 beverage Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000600 sorbitol Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 14
- -1 diol compound Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- BGBUUGMMVYRRLN-UHFFFAOYSA-N P(=O)(O)(O)O.P(=O)(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(=O)(O)(O)O.P(=O)(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C BGBUUGMMVYRRLN-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006698 induction Effects 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
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BNNBECJSDDMHFF-UHFFFAOYSA-N 2,2,3,3-tetramethylcyclobutane-1,1-diol Chemical compound CC1(C)CC(O)(O)C1(C)C BNNBECJSDDMHFF-UHFFFAOYSA-N 0.000 description 1
- LIBOYZGDGVDKKH-UHFFFAOYSA-N 2-(8-methylnonyl)butanedioic acid Chemical compound CC(C)CCCCCCCC(C(O)=O)CC(O)=O LIBOYZGDGVDKKH-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- ZGYHBLSTEXSDOB-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;titanium Chemical compound [Ti].OCCN(CCO)CCO.OCCN(CCO)CCO ZGYHBLSTEXSDOB-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- IILWMQMLKMZUAR-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid methane Chemical compound C.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCC(=O)O.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCC(=O)O.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCC(=O)O.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCC(=O)O IILWMQMLKMZUAR-UHFFFAOYSA-N 0.000 description 1
- BJISXPRYXCKVSD-UHFFFAOYSA-J 3-oxobutanoate;titanium(4+) Chemical compound [Ti+4].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O BJISXPRYXCKVSD-UHFFFAOYSA-J 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- PMKKXYIGCYGBDK-UHFFFAOYSA-N OCC1CCCCC1CO.OCC1CCCCC1CO Chemical compound OCC1CCCCC1CO.OCC1CCCCC1CO PMKKXYIGCYGBDK-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000003712 decolorant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical group 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- VSIGYUOJAOCSKU-UHFFFAOYSA-N methyl 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OC VSIGYUOJAOCSKU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本申請案主張享有2011年1月31號申請之韓國專利申請案第10-2011-0009405號之優先權，該韓國專利申請案所有揭示內容係以引用方式併入本案中。
本發明關於一種聚酯樹脂組成物及該聚酯樹脂組成物之製備方法，且更明確言之，係關於一種與異山梨醇共聚而成並具有優秀顏色安定性(透明度)的聚酯樹脂組成物，及該聚酯樹脂組成物之製備方法。
聚酯樹脂早已廣泛用於封裝材料、物件和薄膜領域中，且為不含內分泌干擾素的環境友善塑膠之一。近來，有關用於作為食物用耐熱容器的聚碳酸酯，經證實雙酚-A(bisphenol-A)對人體有害，並提升對環境友善、透明且耐熱之聚酯樹脂的需求。聚酯樹脂係由至少兩種二醇類(glycol)或二羧酸類(dicarboxylic acid)成分所共聚而成，該聚酯樹脂已商業化地廣泛用於增進樹脂之造模性及去除樹脂的結晶性。於僅使用對苯二甲酸(terephthalic acid)與乙二醇(ethylene glycol)聚合成同元聚酯的情況下，可藉由拉伸誘導結晶和熱固法增進材料性質及材料之耐熱性。然而，在應用與增進耐熱性上有些限制。於使用至少兩種二醇類或對苯二甲酸成分共聚合成聚酯的情況下，缺點在於難以藉由拉伸或結晶法增進該聚酯之耐熱性。已知另一種增進該聚酯之耐熱性的方法，是使用異山梨醇(又名1,4:3,6-二脫水葡萄糖醇)作為其中一種單體，異山梨醇係一種源自澱粉的環境友善性二醇化合物。
美國專利案第5,959,066號揭示一種藉由使用對苯二甲酸或對苯二甲酸二甲酯(dimethylterephthalate)與包含異山梨醇之各種二醇類進行熔融聚合以製備具有0.35 dl/g或更高固有黏度之聚酯的方法。具有0.35 dl/g或更高固有黏度的聚酯樹脂係用於光學產品與塗層，且具有0.4 dl/g或更高固有黏度的聚酯樹脂係用於CD，及具有0.5 dl/g或更高固有黏度之聚酯樹脂係用於瓶罐、膜、薄板及射出成形。再者，美國專利案第6,063,464號揭示一種使用包含異山梨醇之二醇類成分進行熔融聚合以製備具有0.15 dl/g或更高固有黏度之聚酯的方法。及，美國專利案第6,656,577號、美國專利案第6,359,070號、美國專利案第6,140,422號等等文獻揭示一種使用該等包含異山梨醇之二醇類成分製備共聚合聚酯樹脂的方法。
上述專利揭示使用一般催化劑藉由所有酸類與包含異山梨醇之二醇類聚合聚酯的方法，然而，此等方法可能造成於聚酯合成或形成期間變黃，因此需要一種具有顏色安定性(透明度)的組成物，以用於一般塑膠。
因此，本發明之目的係提供一種具有優秀顏色安定性(透明度)的共聚合聚酯樹脂組成物及該共聚合聚酯樹脂組成物之製備方法。
為達成此等目的，本發明提供一種共聚合聚酯樹脂組成物，該組成物包含：占95至99.99重量%的共聚合聚酯樹脂，該共聚合聚酯樹脂係由二羧酸成分與包含異山梨醇之二醇成分共聚而成，該共聚合聚酯樹脂具有由源自該等二羧酸成分之二羧酸部分與源自該等二醇成分之二醇部分所形成的交替結構；及占0.01至5重量%的抗氧化劑，該抗氧化劑選自由受阻酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑及上述氧化劑之混合物所構成之群組中。
本發明亦提供一種用於製備共聚合聚酯樹脂組成物的方法，該方法包含以下步驟：於0至10.0 kg/cm2之升高壓力及150至300℃之溫度下，進行二羧酸成分與含有異山梨醇之二醇成分的酯化反應或轉酯化反應持續2至24小時之平均滯留時間；藉由使該酯化反應或該轉酯化反應之產物於400至0.1毫米汞柱(mmHg)的降低壓力及150至300℃的溫度下進行聚縮合反應持續1至24小時之平均滯留時間，以獲得共聚合聚酯樹脂組成物；及於該酯化反應或該聚縮合反應期間添加抗氧化劑，或混合該抗氧化劑與該製成之共聚合聚酯樹脂，以達95至99.99重量%之該共聚合聚酯樹脂與0.01至5重量%之該抗氧化劑混合，該抗氧化劑係選自由受阻酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑及上述抗氧化劑之混合物所構成的群組中。
根據本發明之共聚合聚酯樹脂由於使用異山梨醇作為該共聚合聚酯樹脂之二醇成分，因而具有優秀的耐熱性與衝擊強度，且由於含有抗氧化劑，諸如受阻酚系抗氧化劑、磷系氧化劑、硫醚類氧化劑及該等氧化劑之混合物，因此該共聚合聚酯樹脂具有優秀的顏色安定性(透明度)。
藉由參閱下述詳細說明，將對本發明有更完整的瞭解，且可較佳地理解本發明帶來之諸多優點。
根據本發明之共聚合聚酯樹脂組成物包含由二羧酸成分與含有異山梨醇之二醇成分共聚而成的共聚合聚酯樹脂及抗氧化劑，該共聚合聚酯樹脂具有由源自該等二羧酸成分之二羧酸部分與源自該等二醇成分之二醇部分所形成的交替結構，該抗氧化劑係選自於由受阻酚系抗氧化劑(hindered phenolic antioxidant)、磷系抗氧化劑(phosphitic antioxidant)、硫醚系抗氧化劑(thioetheric antioxidant)及上述氧化劑之混合物所構成的群組中。
可使用傳統用於製備聚酯樹脂的習知二羧酸成分，作為本發明中所使用的該等二羧酸成分。例如，可使用的二羧酸成分係例如8至20個碳數且較佳8至14個碳數之芳族二羧酸成分、4至20個碳數且較佳4至12個碳數之脂肪族二羧酸成分及上述二羧酸成分之混合物。該等芳族二羧酸成分之詳細實例包括對苯二甲酸(terephthalic acid)、間苯二甲酸(isophthalic acid)、萘二甲酸(naphthalenedicarboxylic acid，例如2,6-萘二甲酸)、聯苯二甲酸(diphenyldicarboxylic acid)，等等。脂肪族二羧酸成份之詳細實例包括線性、分枝狀或環狀脂肪族二羧酸成分，例如環己二甲酸(cyclohexanedicarboxylic acid，例如1,4-環己二甲酸、1,3-環己二甲酸，等等)、鄰苯二甲酸(phthalic acid)、癸二酸(sebasic acid)、丁二酸(succinic acid)、異癸基丁二酸(isodecylsuccinic acid)、順丁烯二酸(maleic acid)、反丁烯二酸(fumaric acid)、己二酸(adipic acid)、戊二酸(glutaric acid)、壬二酸(azelaic acid)，等等。可同時使用該等二羧酸成分之一者或多者。例如，可單獨使用對苯二甲酸或1,4-環己二甲酸，或可使用除對苯二甲酸或1,4-環己二甲酸以外的多種二羧酸成分，作為共聚合的二羧酸成分(共聚合單體)，以增進所製成之聚酯樹脂的性質。該等用於增進性質之共聚合性二羧酸成分的量占該全部二羧酸成分的0至50莫耳%，較佳0.01至40莫耳%，例如0.1至30莫耳%。若該共聚合性二羧酸成分的量超過該範圍，該聚酯樹脂的該等性質可能無法達到充分改善或甚至惡化。
於本案說明書中，二羧酸成分之用語包含二羧酸成分(dicarboxylic acid component，例如，對苯二甲酸)、該等二羧酸成分之烷基酯(1至4個碳數之低階烷基酯，例如單甲基酯、單乙基酯、二甲基酯、二乙基酯或二丁基酯)、該等二羧酸成分之酸酐，等等，當與乙二醇(二醇)成分反應時，該等二羧酸成分能提供二羧酸部分，例如對苯二甲酸部分。又，於本案說明書中，該二羧酸部分或二醇部分代表於該等二羧酸成分與該等二醇成分之聚合反應中移除氫、羥基或烷氧基後所餘留的殘基。
本發明中所使用之該等二醇成分必定含有占該總二醇成分之1至60莫耳%、較佳4至40莫耳%、更佳10至30莫耳%的異山梨醇(1,4:3,6-二脫水葡萄糖醇)。可使用傳統用於製備聚酯樹脂的習知二醇成分作為該等二醇成分的該等其餘成分(共聚合性二醇成分、共聚合性單體)。該等共聚合性二醇成分的量係占該總二醇成分之40至99莫耳%、較佳60至96莫耳%、更佳70至90莫耳%。例如，作為該等二醇成分之其餘成分，可使用的二醇成分係例如8至40個且較佳8至33個碳數的芳族二醇成分、2至20個且較佳2至12個碳數的脂肪族二醇成分，及上述二醇成份之混合物。該等芳族二醇成分之詳細實例包括：經環氧乙烷及/或環氧丙烷加成的雙酚A衍生物(聚氧伸乙基-(n)-2,2-雙(4-羥苯基)丙烷(polyoxyethylene-(n)-2,2-bis(4-hydroxyphenyl)propane)、聚氧伸丙基-(n)-2,2-雙(4-羥苯基)丙烷(polyoxypropylene-(n)-2,2-bis(4-hydroxyphenyl)propane)或聚氧伸丙基-(n)-聚氧伸乙基-(n)-2,2-雙(4-羥苯基)丙烷(polyoxyethylene-(n)-polyoxyethylene-(n)-2,2-bis(4-hydroxyphenyl)propane),(其中n代表聚氧伸乙基單元或聚氧伸丙基單元的數目)，例如聚氧伸乙基-(2.0)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(2.0)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(2.2)-聚氧伸乙基-(2.0)-2,2-雙(4-羥苯基)丙烷、聚氧伸乙基-(2.3)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(6)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(2.3)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(2.4)-2,2-雙(4-羥苯基)丙烷、聚氧伸丙基-(3.3)-2,2-雙(4-羥苯基)丙烷、聚氧伸乙基-(3.0)-2,2-雙(4-羥苯基)丙烷、聚氧伸乙基-(6)-2,2-雙(4-羥苯基)丙烷，及諸如此類者。該等脂肪族二醇成分之詳細實例包括：線性、分枝狀或環狀脂肪族二醇成分，例如乙二醇(ethylene glycol)、一縮二乙二醇(diethylene glycol)、二縮三乙二醇(triethylene glycol)、丙二醇(propanediol，例如1,2-丙二醇、1,3-丙二醇及諸如此類者)、1,4-丁二醇、戊二醇、己二醇(1,6-己二醇及諸如此類者)、辛戊二醇(2,2-二甲基-1,3-丙二醇)、1,2-環己二醇(1,2-cyclohexanediol)、1,4-環己二醇(1,4-cyclohexanediol)、1,2-環己二甲醇(1,2-cyclohexanedimethanol)、1,3-環己二甲醇(1,3-cyclohexanedimethanol)、1,4-環己二甲醇(1,4-cyclohexanedimethanol)、四甲基環丁二醇(tetramethylcyclobutanediol)及諸如此類者。同時可使用除異山梨醇以外的一或多種共聚合性二醇成分，作為該等二醇成分。例如，選自乙二醇、1,4-環己二甲醇、聚氧伸乙基-(2.0)-2,2-雙(4-羥苯基)丙烷所構成之群組中的至少一者添加於該異山梨醇中。特別是使用1,4-環己二甲醇作為共聚合二醇成分的情況下，當1,4-環己二甲醇的量提高時，該經共聚合之聚酯樹脂的衝擊強度迅速提高。相對於總二醇成分而言，若異山梨醇的量少於1莫耳%或該等共聚合性二醇成分的量高於99莫耳%，該共聚合聚酯樹脂的耐熱性可能不足；及相對於總二醇成分而言，若異山梨醇的量高於60莫耳%或該等共聚合性二醇成分的量少於40莫耳%，該共聚合聚酯樹脂或產品的顏色可能變黃。
本發明中所使用之共聚合聚酯樹脂係由該等二羧酸成分與該等二醇成分所共聚合而成，且以鄰氯酚(OCP)溶解該共聚合聚酯樹脂，使該共聚合聚酯樹脂達1.2 g/dl之濃度後，於35℃溫度下展現0.15 dl/g或更高、較佳0.5 dl/g或更高、更佳0.7 dl/g或更高的固有黏度。由本發明聚酯樹脂製備成3.2毫米厚之測試樣品的缺口耐衝擊強度(ASTM D256法、測量溫度：23℃)經測量係較佳50 J/m或更高。且經300℃退火處理5分鐘並冷卻至室溫後，以10℃/分鐘之升溫速度於再加熱期間(第二次掃描)測量本發明之聚酯樹脂的玻璃轉化溫度(Tg)係較佳90℃或更高。
本發明中所使用的抗氧化劑係用於提高本發明之共聚合聚酯樹脂組成物的顏色安定性(透明度)，且於該共聚合聚酯樹脂之聚合期間或聚合之後藉由混合使該共聚合聚酯樹脂組成物中含有該抗氧化劑。該抗氧化劑可使用受阻酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑、上述氧化劑之混合物及諸如此類者。
該受阻酚系抗氧化劑之代表性實例包括1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羥苄基)苯(1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)、1,6-雙[3-(3,5-二-叔丁基-4-羥苯基)丙醯胺基]己烷(1,6-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane)、1,6-雙[3-(3,5-二-叔丁基-4-羥苯基)丙醯胺基]丙烷(1,6-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane)、四[伸甲基(3,5-二-叔丁基-4-羥基氫化肉桂酸酯)]甲烷(tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane)及諸如此類者。
可使用式1所示之化合物作為該磷系抗氧化劑。
於該式1中，R1及R2獨立地為經取代或未經取代之1至30個(較佳1至20個)碳原子的烷基，或經取代或未經取代之6至30個(較佳6至20個)碳原子的芳基。該磷系抗氧化劑之代表性實例包括雙(2,6-二-叔丁基-4-甲基苯基)季戊四醇-二-磷酸酯(bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite)、雙(2,4-二-叔丁基苯基)季戊四醇-二-磷酸酯(bis(2,4-di-tert-butylphenyl)pentraerythritol-di-phosphite)及諸如此類者。
可使用式2或式3所示之化合物作為該硫醚系抗氧化劑。
於該式2或式3中，R3及R4獨立為經取代或未經取代之1至30個(較佳1至20個)碳原子的烷基，或經取代或未經取代之6至30個(較佳6至20個)碳原子的芳基。該硫醚系抗氧化劑之代表性實例包括四[甲基-3-(十二烷基硫代)丙酸酯]甲烷(tetrakis[methane-3-(laurylthio)propionate]methane)、硫二丙酸二(十八烷酯)(distearyl thiodipropionate)、硫二丙酸二月桂酯(dilauryl thiodipropionate)，等等。
本發明之共聚合聚酯樹脂組成物包含95至99.99重量%(較佳96至99重量%)的該共聚合聚酯樹脂及0.01至5重量%(較佳1至4重量%)的該抗氧化劑。相對於該總共聚合聚酯樹脂組成物而言，若該共聚合聚酯樹脂的量少於95重量%或該抗氧化劑的量高於5重量%，可能發生混濁情形且透明度可能變差。相對於該總共聚合聚酯樹脂組成物而言，若該共聚合聚酯樹脂的量高於99.99重量%或該抗氧化劑的量高於0.01重量%，該共聚合聚酯樹脂組成物可能發生變黃情形且顏色安定性(透明度)變差。
本發明之共聚合聚酯樹脂具有優秀的顏色安定性(透明度)、耐熱性和衝擊強度，且適合用於製造聚酯樹脂物件，該聚酯樹脂物件係選自膜、薄板、飲料瓶、奶瓶、纖維、光學產品及諸如此類者所構成之群組中。
以下將描述用於製備本發明之聚酯樹脂的方法。首先，(a)使該等二羧酸成分與該等含有異山梨醇之二醇成分於0至10.0kg/cm2之升高壓力及150至300℃的溫度下進行酯化反應或轉酯化反應持續1至24小時之平均滯留時間。且，(b)使該酯化反應或該轉酯化反應之產物於400至0.01毫米汞柱的降低壓力及150至300℃的溫度下進行聚縮合反應持續1至24小時之平均滯留時間，以產生該共聚合聚酯樹脂。隨後，(c)藉由添加抗氧化劑，如藉由於該酯化反應或該聚縮合反應期間添加抗氧化劑，或藉由混合該抗氧化劑與該製成之共聚合聚酯樹脂，達到使95至99.99重量%之該共聚合聚酯樹脂與0.01至5重量%之該抗氧化劑混合，而能製備出本發明之共聚合聚酯樹脂組成物，其中該抗氧化劑係選自受阻酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑及上述抗氧化劑之混合物所構成之群組中。其中，較佳係於惰性氣體環境下進行該酯化反應及該轉酯化反應，且該共聚合聚酯樹脂與該氧化劑之混合步驟可為簡單混合或透過擠出動作而混合。
現將更詳細說明用於製備本發明之共聚合聚酯樹脂組成物的聚合條件。為製備該含有異山梨醇的共聚合聚酯樹脂，首先使該等包含異山梨醇之總二醇(甘醇)成分與該等包含對苯二甲酸及諸如此類者之總二羧酸成分的莫耳比值控制在1.05至3.0，較佳為1.1至2.0，更佳為1.2至1.8，且於150至300℃(較佳為200至270℃，更佳為240至260℃)的溫度下且於0至10.0 kg/cm2(較佳為0至5.0 kg/cm2，更佳為0.1至3.0 kg/cm2)之壓力下進行酯化反應。其中，若該等二醇成分/二羧酸成分的莫耳比值小於1.05，在該聚合反應期間可能有未反應的剩餘二羧酸成分，未反應的剩餘二羧酸成分會造成該樹脂透明度變差。若該等二醇成分/二羧酸成分的莫耳比值大於3.0，該聚合反應速率可能減低，且該樹脂的產率可能無法令人滿意。此外，若溫度和壓力超出該範圍，該共聚合聚酯樹脂的性質可能變差。該酯化反應的反應時間(平均滯留時間)通常為1至24小時，較佳為2至8小時，且該時間能根據反應溫度、反應壓力及該等甘醇成分相對於該等二羧酸成份之莫耳比值而改變。
該用於製備共聚合聚酯樹脂的製程可分成酯化反應((a)步驟)及聚縮合反應((b)步驟)。該酯化反應無需觸媒，但可使用觸媒以縮短反應時間。可以批次製程或連續製程執行該酯化反應((a)步驟)。每種反應物可個別注入反應器內，但較佳係將該等二醇成分與該等二羧酸成分的混合物漿料注入該反應器內。其中，可使用水或乙二醇溶解在室溫下呈固態的該等甘醇成分(例如異山梨醇)，且接著與該等二羧酸成分(例如對苯二甲酸)混合而形成漿料。或者，可將水加入含有二羧酸成分和共聚合性甘醇成分(例如異山梨醇及乙二醇)的漿料中以提高異山梨醇之溶解度，或可於60℃或更高的升高溫度下製備該漿料，使得異山梨醇熔化於該漿料中。
該酯化反應((a)步驟)完成後，進行該聚縮合反應((b)步驟)。於該聚縮合反應((b)步驟)起始之前，可於該酯化反應或轉酯化反應的產物中添加聚縮合觸媒、安定劑、脫色劑及其他添加物。該聚縮合觸媒的實例包括習知的鈦系觸媒、鍺系觸媒、銻系觸媒、鋁系觸媒、錫系觸媒及上述觸媒之混合物。該較佳鈦系觸媒的實例包括鈦酸四乙酯(tetraethyl titanate)、乙醯鈦酸三丙酯(acetyltripropyl titanate)、鈦酸四丙酯(tetrapropyl titanate)、鈦酸四丁酯(tetrabutyl titanate)、聚鈦酸丁酯(polybutyl titanate)、鈦酸2-乙基己酯(2-ethylhexyl titanate)、鈦酸辛二醇酯(octylene glycol titanate)、乳酸鹽合鈦(lactate titanate)、三乙醇胺鈦酸酯(triethanolamine titanate，或稱鈦酸次氮基三乙酯)、乙醯丙酮合鈦(Titanium acetylacetonate)、乙醯乙酸乙酯合鈦(titanium ethyl acetoacetate)、鈦酸異十八烷基酯(isostearyl titanate)、二氧化鈦、二氧化鈦/二氧化矽之共沉澱物、二氧化碳/二氧化鋯之共沉澱物及諸如此類者。及，較佳鍺系觸媒之實例包括二氧化鍺及二氧化鍺之共沉澱物。通常，可使用磷系安定劑，例如磷酸、磷酸三甲酯(trimethyl phosphate)、磷酸三乙酯(triethyl phosphate)及諸如此類者，作為用於該聚縮合反應的安定劑。關於該安定劑的的量，相對於所製成之聚酯樹脂(共聚合聚酯樹脂)的總重量而言，該磷系安定劑的量係10至100 ppm。若該磷系安定劑的量少於10 ppm，該聚酯樹脂可能不夠安定，且該聚酯樹脂的顏色可能變黃。若該磷系安定劑的量高於100 ppm，該聚酯樹脂的聚合度可能不足。用於改善該聚酯樹脂之顏色性質的脫色劑實例包括習知的脫色劑，例如乙酸鈷、丙酸鈷及諸如此類者。如必要，可使用有機脫色劑做為該脫色劑。相對於所製成之聚酯樹脂的總重量而言，該脫色劑的較佳用量係0至100 ppm。通常，於150至300℃(較佳為200至290℃，更佳為260至280℃)的溫度下且於400至0.01毫米汞柱(較佳為100至0.05毫米汞柱，更佳為10至0.1毫米汞柱)之降低壓力下進行該聚縮合反應。維持該400至0.01毫米汞柱之降低壓力，以去除該聚縮合反應的副產物-甘醇。因此，若該降低壓力超過該範圍，可能無法有效去除該副產物。此外，若該聚縮合反應溫度超過該範圍，該共聚合聚酯樹脂的性質可能變差。該聚縮合反應持續進行直到獲得該聚酯樹脂之期望的固有黏度，例如該聚縮合反應可持續進行1至24小時的平均滯留時間。
最後，能藉由於該酯化反應或於該聚縮合反應期間加入抗氧化劑，或混合該抗氧化劑與所製成之共聚合聚酯樹脂，而製備出本發明之共聚合聚酯樹脂組成物。
以下提供數個較佳實例以求更佳地理解本發明。然而，本發明不限於下列實例。
於下列實例及對照例中，TPA、AA、CHDA、ISB、CHDM、EG和BPA-EO分別代表對苯二甲酸、己二酸、1,4-環己烷二甲酸、異山梨醇(1,4:3,6-二脫水葡萄糖醇)、1,4-環己烷二甲醇、乙二醇及聚氧伸乙基-(2.0)-2,2-雙(4-羥苯基)丙烷，且對聚合物進行性能評估的方法如下述。
(1) 固有黏度(IV)：於150℃使該聚合物溶解於鄰氯酚(OCP)中達0.12%之濃度之後，在35℃之恆溫器中使用Ubbelohde黏度計測量該聚合物之固有黏度(IV)。
(2) 耐熱性(玻璃-橡膠轉化溫度，Tg)：使該聚酯樹脂於300℃下退火5分鐘並冷卻至室溫後，以10℃/分鐘之升溫速度於第二次掃描期間測量該聚酯樹脂的玻璃轉化溫度(Tg)。
(3) 顏色安定性(顏色L及顏色b)：使用太平洋科技公司(Pacific Scientific Company)之Colorgard系統測量該顏色L和顏色b。
(4) 混濁度(%)：使該聚酯樹脂置於23℃與65%相對濕度下老化24小時，使用濁度計(日本，Nippon Denshoku公司，品名：NDH2000)依照JIS(日本工業標準)K7136法測量該共聚合聚酯樹脂之薄膜樣品三個獨立位置處的混濁度(%)，且計算每次測量結果之平均值以作為最後結果值。
根據表1中所述之量，於7公升體積之反應器中加入反應物，並依據每種主要元素的原子添加200ppm之鍺系觸媒、70ppm之磷系安定劑和50ppm之鈷系脫色劑。及，加熱該反應器達240至300℃，以進行酯化反應。待副產物「水」流出而達70至99重量%之後，開始進行聚縮合反應，且達某黏度時終止該反應。測量該共聚合聚酯樹脂之固有黏度(IV)、耐熱性(Tg)、顏色L和顏色b，且該等數據列示於表1中。
根據表1之該等組成製備共聚合聚酯樹脂。除了在製備共聚合聚酯樹脂期間或之後，混合至少一種下述抗氧化劑：四[伸甲基(3,5-二-叔丁基-4-羥基氫化肉桂酸酯)]甲烷(AO1)、雙(2,6-二-叔丁基-4-甲基苯基)季戊四醇-二-磷酸酯(AO2)及四[甲基-3-(十二烷基硫代)丙酸酯]甲烷(AO3)(依據該共聚合聚酯樹脂組成物總量添加該等抗氧化劑(ppm))以外，係使用對照例1中所述之相同方式製備聚酯樹脂組成物。測量該共聚合聚酯樹脂之固有黏度(IV)、耐熱性(Tg)、顏色L和顏色b，且該等數據列示於表1中。
於表1中，二羧酸成分與二醇成分的比例(%)係所產生之共聚合聚酯樹脂中所含的二羧酸成分與二醇成分之比例，並藉由核磁共振分析法(NMR分析法)鑑定該成分比例。如表1所示，相較於習知共聚合聚酯樹脂(對照例1至3)，根據本發明之該等含有抗氧化劑的聚酯樹脂組成物(實施例1至6)具有相對優秀的顏色安定性(顏色L和顏色b)。然而，若抗氧化劑的量相對於該共聚合聚酯樹脂組成物總量而言超過5重量%(對照例4)，該反應速率將會極慢，而無法獲得具有期望聚合度(大於1.5 dl/g)的共聚合聚酯樹脂組成物。
根據表2，使對照例1至3中所製備的該等共聚合聚酯樹脂於1托耳(torr)之真空中且於40℃下減壓並乾燥6小時，且隨後在表2所列之擠出溫度下從直徑20毫米且具有T形模(T-die)之雙螺桿式擠出機將該等共聚合聚酯樹脂擠製成薄板。於冷卻至5℃的模鑄鼓(drum)上以靜電感應鑄造法製造該等聚酯樹脂物件(薄板)。測量該等薄板之顏色L、顏色b及混濁度(%)，且該等數據列示於表2。
根據表2，使對照例1至3中所製備的該等共聚合聚酯樹脂與下列至少一種抗氧化劑冰溫混合：四[伸甲基(3,5-二-叔丁基-4-羥基氫化肉桂酸酯)]甲烷(AO1)、雙(2,6-二-叔丁基-4-甲基苯基)季戊四醇-二-磷酸酯(AO2)及四[甲基-3-(十二烷基硫代)丙酸酯]甲烷(AO3)，且於1托耳之真空中在40℃下減壓並乾燥6小時，及隨後在表2所列之擠出溫度下從直徑20毫米之具有T形模(T-die)的雙螺桿式擠出機將該等共聚合聚酯樹脂擠製成薄板。於冷卻至5℃的模鑄鼓上以靜電感應鑄造法製造該等聚酯樹脂物件(薄板)。測量該等薄板之顏色L、顏色b及混濁度(%)，且該等數據列示於表2。
(A：於對照例1中所製備之共聚合聚酯樹脂，B：於對照例2中所製備之共聚合聚酯樹脂，C：於對照例3中所製備之共聚合聚酯樹脂)
如表2所示，相較於樹脂中沒有混合抗氧化劑的習知聚酯樹脂物件(薄板，對照例5至7)，根據本發明之該等聚酯樹脂物件(實施例7至13)具有相對優秀的顏色安定性(顏色L和顏色b)。
Claims (11)
- 一種共聚合聚酯樹脂組成物，該組成物包含：占95至99.99重量%的一共聚合聚酯樹脂，該共聚合聚酯樹脂係由二羧酸成分與包含異山梨醇之二醇成分共聚而成，該共聚合聚酯樹脂具有由源自該等二羧酸成分之二羧酸部分與源自該等二醇成分之二醇部分所形成的一交替結構；及占0.01至5重量%的一抗氧化劑，該抗氧化劑選自由一受阻酚系抗氧化劑、一磷系抗氧化劑、一硫醚系抗氧化劑及上述氧化劑之混合物所構成之一群組中，其中該等二醇成分包含1至60莫耳%的異山梨醇以及40至99莫耳%的1,4-環己二甲醇，且該共聚合聚酯樹脂的玻璃轉化溫度(Tg)為90℃或更高。
- 如請求項1之共聚合聚酯樹脂組成物，其中該等二羧酸成分係選自於由8至20個碳數之芳族二羧酸成分、4至20個碳數之脂肪族二羧酸成分及上述二羧酸成份之混合物所構成的一群組中。
- 如請求項1之共聚合聚酯樹脂組成物，其中該磷系抗氧化物係式1所示一化合物，
- 如請求項1之共聚合聚酯樹脂組成物，其中該硫醚系抗氧化劑係式2或式3所示之一化合物，
- 如請求項1之共聚合聚酯樹脂組成物，其中以鄰氯酚(orthochlorophenol)溶解該共聚合聚酯樹脂，使該共聚合聚酯樹脂達1.2g/dl之濃度後，該共聚合聚酯樹脂於35℃之溫度下具有0.15dl/g或更高的固有黏度。
- 一種使用如請求項1至5項任一項之共聚合聚酯樹脂組成物所製成的聚酯樹脂物件，該聚酯樹脂物件係選自由一膜、一薄板、一飲料瓶、一奶瓶、一纖維及一光學 產品所構成之該群組中。
- 一種用於製備共聚合聚酯樹脂組成物的方法，該方法包含下述步驟：於0至10.0kg/cm2之升高壓力及150至300℃之溫度下，進行二羧酸成分與含有異山梨醇之二醇成分的一酯化反應或轉酯化反應持續2至24小時之平均滯留時間；藉由使該酯化反應或該轉酯化反應之產物於400至0.1毫米汞柱的降低壓力及150至300℃的溫度下進行一聚縮合反應持續1至24小時之平均滯留時間，以獲得一共聚合聚酯樹脂組成物；及於該酯化反應或該聚縮合反應期間添加一抗氧化劑，或混合該抗氧化劑與該製成之共聚合聚酯樹脂，以達95至99.99重量%之該共聚合聚酯樹脂與0.01至5重量%之該抗氧化劑混合，該抗氧化劑係選自由一受阻酚系抗氧化劑、一磷系抗氧化劑、一硫醚系抗氧化劑及上述抗氧化劑之混合物所構成之一群組中，其中該等二醇成分包含1至60莫耳%的異山梨醇以及40至99莫耳%的1,4-環己二甲醇，且該共聚合聚酯樹脂的玻璃轉化溫度(Tg)為90℃或更高。
- 如請求項7之用於製備共聚合聚酯樹脂組成物的方法，其中該二羧酸成分係選自由8至20個碳數之芳族二羧酸成分、4至20個碳數之脂肪族二羧酸成分及上述二 羧酸成份之混合物所構成的一群組中。
- 如請求項7之用於製備共聚合聚酯樹脂組成物的方法，其中該磷系抗氧化劑係式1所示之一化合物，
- 如請求項7之用於製備共聚合聚酯樹脂組成物的方法，其中該硫醚系抗氧化劑係式2或式3所示之一化合物，
- 如請求項7之用於製備共聚合聚酯樹脂組成物的方 法，其中以鄰氯酚溶解該共聚合聚酯樹脂，使該共聚合聚酯樹脂達1.2g/dl之濃度後，該共聚合聚酯樹脂於35℃之溫度下具有0.15dl/g或更高的固有黏度。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110009405A KR101796764B1 (ko) | 2011-01-31 | 2011-01-31 | 공중합 폴리에스테르 수지 조성물 및 그 제조방법 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201231497A TW201231497A (en) | 2012-08-01 |
| TWI588176B true TWI588176B (zh) | 2017-06-21 |
Family
ID=46603190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101103077A TWI588176B (zh) | 2011-01-31 | 2012-01-31 | 聚酯樹脂組成物及其製備方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9388309B2 (zh) |
| EP (1) | EP2671922B1 (zh) |
| JP (1) | JP5989676B2 (zh) |
| KR (1) | KR101796764B1 (zh) |
| CN (2) | CN107652634A (zh) |
| TW (1) | TWI588176B (zh) |
| WO (1) | WO2012105770A2 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI804171B (zh) * | 2021-02-05 | 2023-06-01 | 南韓商愛思開邁克沃股份有限公司 | 聚酯樹脂丸粒、聚酯薄膜及其製備方法 |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101639631B1 (ko) * | 2009-12-28 | 2016-07-14 | 에스케이케미칼주식회사 | 장식 물질을 포함하는 열가소성 성형제품 |
| MX2015016050A (es) * | 2013-05-21 | 2016-06-21 | Ester Ind Ltd | Tereftalato de polietileno resistente al calor y un proceso para prepararlo. |
| KR101995907B1 (ko) * | 2013-07-24 | 2019-07-03 | 에스케이케미칼 주식회사 | 고내열 고투명 폴리카보네이트 에스테르 및 그 제조방법 |
| US9745415B2 (en) * | 2014-02-21 | 2017-08-29 | Ester Industries Limited | Sulfonated co-polyesters and method for manufacturing |
| CN108473667A (zh) | 2015-12-24 | 2018-08-31 | Sk化学株式会社 | 聚酯树脂、其制备方法以及由其形成的树脂模制物品 |
| KR102670942B1 (ko) * | 2016-02-04 | 2024-05-31 | 에스케이케미칼 주식회사 | 내열성 및 용제 용해성이 우수한 폴리에스테르 수지 및 이를 함유하는 코팅 조성물 |
| FR3052454B1 (fr) * | 2016-06-10 | 2018-06-29 | Roquette Freres | Polyester thermoplastique amorphe pour la fabrication de corps creux |
| US11447603B2 (en) * | 2017-05-31 | 2022-09-20 | Sk Chemicals Co., Ltd. | Polyester resin, method for preparing same, and resin molded product formed therefrom |
| KR102568693B1 (ko) * | 2017-06-02 | 2023-08-21 | 에스케이케미칼 주식회사 | 폴리에스테르 섬유, 이의 제조 방법 및 이로부터 형성된 성형체 |
| CN110573551B (zh) | 2017-06-22 | 2022-02-15 | Sk化学株式会社 | 聚酯容器及其制造方法 |
| KR102684863B1 (ko) * | 2017-06-26 | 2024-07-15 | 에스케이케미칼 주식회사 | 폴리에스테르 필름 및 이의 제조 방법 |
| TWI626256B (zh) * | 2017-06-30 | 2018-06-11 | 財團法人工業技術研究院 | 合成非晶形共聚酯的觸媒組成物及製備方法 |
| TWI664186B (zh) * | 2017-10-05 | 2019-07-01 | 遠東新世紀股份有限公司 | 磷酸酯物質及其製備方法、含磷酸酯物質的聚酯樹脂及其製備方法 |
| JP2020033681A (ja) * | 2018-03-13 | 2020-03-05 | 東レ株式会社 | 吸湿性に優れた海島型複合繊維、繊維構造体およびポリエステル組成物 |
| KR102036284B1 (ko) | 2019-06-21 | 2019-10-24 | 이규득 | 폴리에틸렌 테레프탈레이트 필름의 제조방법 |
| KR102038694B1 (ko) | 2019-08-12 | 2019-10-31 | 금강기업 주식회사 | 비결정성 폴리에틸렌 테레프탈레이트 필름의 제조방법 |
| KR102210711B1 (ko) * | 2019-10-30 | 2021-02-03 | 주식회사 삼양사 | 무수당 알코올과 무수당 알코올-알킬렌 글리콜을 포함하는 생분해성 공중합 폴리에스테르 수지 및 이의 제조 방법 |
| US20230105592A1 (en) * | 2020-06-01 | 2023-04-06 | Toray Advanced Materials Korea Inc. | Organic solvent-soluble copolymer polyester, composition for forming ultrafiltration membrane comprising same, and high water permeability reverse osmosis membrane prepared therefrom |
| CN117897429B (zh) * | 2021-05-14 | 2024-10-29 | 丹尼米尔知识产权有限责任公司 | 聚酯抗冲击改性剂 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047098A (zh) * | 1989-05-08 | 1990-11-21 | 汎塑料株式会社 | 聚酯树脂组合物及其模制品 |
| US20040092703A1 (en) * | 2002-11-13 | 2004-05-13 | Germroth Ted Calvin | Method for making isosorbide containing polyesters |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS558023B2 (zh) * | 1975-02-27 | 1980-03-01 | ||
| US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
| US6140422A (en) | 1998-04-23 | 2000-10-31 | E.I. Dupont De Nemours And Company | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
| US6025061A (en) * | 1998-04-23 | 2000-02-15 | Hna Holdings, Inc. | Sheets formed from polyesters including isosorbide |
| US5959066A (en) | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
| WO2001070846A1 (fr) | 2000-03-22 | 2001-09-27 | Dainippon Ink And Chemicals, Inc. | Antichoc et composition polyester contenant ledit antichoc |
| US6656577B1 (en) | 2002-06-14 | 2003-12-02 | E. I. Du Pont De Nemours & Company | Process for making poly(ethylene-co-isosorbide) terephthalate polymer |
| JP2006070101A (ja) * | 2004-08-31 | 2006-03-16 | Mitsubishi Chemicals Corp | ポリエステル樹脂および樹脂組成物ならびに延伸ブロー成形用プリフォーム及び中空容器 |
| US20060173154A1 (en) * | 2004-09-14 | 2006-08-03 | Charbonneau Larry F | Process for making low color poly(ethylene-co-isosorbide) terephthalate polymer |
| JP2008156616A (ja) * | 2006-11-28 | 2008-07-10 | Toray Ind Inc | 樹脂組成物およびそれからなる成形品 |
| JP5377869B2 (ja) * | 2008-03-07 | 2013-12-25 | ウィンテックポリマー株式会社 | 難燃性樹脂組成物及び被覆電線 |
-
2011
- 2011-01-31 KR KR1020110009405A patent/KR101796764B1/ko active Active
-
2012
- 2012-01-30 CN CN201710779302.7A patent/CN107652634A/zh active Pending
- 2012-01-30 US US13/979,513 patent/US9388309B2/en active Active
- 2012-01-30 JP JP2013552458A patent/JP5989676B2/ja active Active
- 2012-01-30 WO PCT/KR2012/000669 patent/WO2012105770A2/ko not_active Ceased
- 2012-01-30 EP EP12742576.7A patent/EP2671922B1/en active Active
- 2012-01-30 CN CN2012800070130A patent/CN103339194A/zh active Pending
- 2012-01-31 TW TW101103077A patent/TWI588176B/zh active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047098A (zh) * | 1989-05-08 | 1990-11-21 | 汎塑料株式会社 | 聚酯树脂组合物及其模制品 |
| US20040092703A1 (en) * | 2002-11-13 | 2004-05-13 | Germroth Ted Calvin | Method for making isosorbide containing polyesters |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI804171B (zh) * | 2021-02-05 | 2023-06-01 | 南韓商愛思開邁克沃股份有限公司 | 聚酯樹脂丸粒、聚酯薄膜及其製備方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012105770A2 (ko) | 2012-08-09 |
| JP2014507531A (ja) | 2014-03-27 |
| JP5989676B2 (ja) | 2016-09-07 |
| EP2671922A2 (en) | 2013-12-11 |
| US9388309B2 (en) | 2016-07-12 |
| CN103339194A (zh) | 2013-10-02 |
| US20130295306A1 (en) | 2013-11-07 |
| KR101796764B1 (ko) | 2017-11-10 |
| EP2671922A4 (en) | 2016-08-31 |
| WO2012105770A3 (ko) | 2012-12-20 |
| TW201231497A (en) | 2012-08-01 |
| CN107652634A (zh) | 2018-02-02 |
| KR20120088209A (ko) | 2012-08-08 |
| EP2671922B1 (en) | 2020-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI588176B (zh) | 聚酯樹脂組成物及其製備方法 | |
| CA2773244C (en) | Polyester resin and method for preparing the same | |
| CN1250600C (zh) | 具有增大的玻璃化转变温度的低熔体粘度的无定形共聚聚酯 | |
| TWI551650B (zh) | 聚酯及聚碳酸酯的混合物 | |
| TWI494367B (zh) | 聚乳酸樹脂與共聚酯樹脂之摻合物及使用該摻合物之物品 | |
| KR20100023856A (ko) | 2,2,4,4-테트라메틸-1,3-사이클로뷰탄다이올 및 1,4-사이클로헥산다이메탄올을 기제로 한 코폴리에스터의 제조 방법 | |
| KR101551562B1 (ko) | 1,4-시클로헥산디메탄올이 공중합된 폴리에스테르 수지 조성물 | |
| KR102675032B1 (ko) | 폴리에스테르 수지 및 이의 제조방법 | |
| JP7369178B2 (ja) | ポリエステル樹脂およびその製造方法 | |
| KR20200062615A (ko) | 고분자량의 지방족 카보네이트 및 방향족 에스테르 공중합체 제조방법 | |
| US11312821B2 (en) | Polyester resin and preparation method of the same | |
| KR20230095526A (ko) | 공중합 폴리에스테르 수지 및 이의 제조 방법 | |
| HK1167417B (zh) | 聚酯树脂及其制备方法 | |
| HK1191356A (zh) | 聚酯树脂及其制备方法 |