JPS63277231A - Production of copolyester - Google Patents
Production of copolyesterInfo
- Publication number
- JPS63277231A JPS63277231A JP1365187A JP1365187A JPS63277231A JP S63277231 A JPS63277231 A JP S63277231A JP 1365187 A JP1365187 A JP 1365187A JP 1365187 A JP1365187 A JP 1365187A JP S63277231 A JPS63277231 A JP S63277231A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- carbon atoms
- terminal
- hydrocarbon group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229920001634 Copolyester Polymers 0.000 title claims description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 229920002601 oligoester Polymers 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 230000010933 acylation Effects 0.000 claims description 12
- 238000005917 acylation reaction Methods 0.000 claims description 12
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 16
- -1 terephthalic acid Chemical compound 0.000 abstract description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 2
- 229960001755 resorcinol Drugs 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical group 0.000 description 2
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 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
- 238000000465 moulding Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- XDUKPUDGTQCPFY-UHFFFAOYSA-N (2,5-dihydroxyphenyl) acetate Chemical compound CC(=O)OC1=CC(O)=CC=C1O XDUKPUDGTQCPFY-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- UWUNWZJAUUXNBQ-UHFFFAOYSA-N 2-(dimethylamino)benzene-1,4-diol Chemical compound CN(C)C1=CC(O)=CC=C1O UWUNWZJAUUXNBQ-UHFFFAOYSA-N 0.000 description 1
- BAYSHFQWTRUCAD-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(Cl)C(O)=CC=C1SC1=CC=C(O)C(Cl)=C1 BAYSHFQWTRUCAD-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- YUWKPDBHJFNMAD-UHFFFAOYSA-N 2-fluoroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(F)=C1 YUWKPDBHJFNMAD-UHFFFAOYSA-N 0.000 description 1
- VQBBXLZPRXHYBO-UHFFFAOYSA-N 2-methoxyterephthalic acid Chemical compound COC1=CC(C(O)=O)=CC=C1C(O)=O VQBBXLZPRXHYBO-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- VIIYYMZOGKODQG-UHFFFAOYSA-N 2-nitrobenzene-1,4-diol Chemical compound OC1=CC=C(O)C([N+]([O-])=O)=C1 VIIYYMZOGKODQG-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- PLOUQIGEQKCKHG-UHFFFAOYSA-N 3-Methylazelaic acid Chemical compound OC(=O)CC(C)CCCCCC(O)=O PLOUQIGEQKCKHG-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 101100451954 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) HXT1 gene Proteins 0.000 description 1
- 101000650578 Salmonella phage P22 Regulatory protein C3 Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 101001040920 Triticum aestivum Alpha-amylase inhibitor 0.28 Proteins 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- SQVRNKJHWKZAKO-UHFFFAOYSA-N beta-N-Acetyl-D-neuraminic acid Natural products CC(=O)NC1C(O)CC(O)(C(O)=O)OC1C(O)C(O)CO SQVRNKJHWKZAKO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009835 boiling Methods 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
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- SQVRNKJHWKZAKO-OQPLDHBCSA-N sialic acid Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@](O)(C(O)=O)OC1[C@H](O)[C@H](O)CO SQVRNKJHWKZAKO-OQPLDHBCSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高弾性率および高強度を有する共重合ポリエス
テルの新規な製造法に関するものである。このようにし
て製造された共重合ポリエステルはサーモトロピックな
液晶を形成するので、成形が容易であp、成形材料、フ
ィルム、繊維として製品化出来るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel method for producing a copolyester having high elastic modulus and high strength. Since the copolymerized polyester thus produced forms thermotropic liquid crystal, it can be easily molded and can be commercialized as a molding material, film, or fiber.
近年、繊維、フィルムまたは成形品の何れかを問わず、
!1111性、耐熱性および耐薬品性の優れた素材に対
する要望が高オっている。ポリエステルは、一般成形品
の用途を広く認められるに到っているが、多くのポリエ
ステルは曲げ弾性率、曲げ強度が劣るため、高弾性率、
高強度を要求される用途には適してぃなかった。この機
械的物性を向上させる為に、炭酸カルシウムやガラス繊
維等の補強材をブレンドする方法が知られているが、材
料の比重が大きくなるため、プラスチックの特徴である
軽食の長所が減じ、さらに成形時においては、成形機の
摩耗が激しく、実用上の問題点が多い。In recent years, whether fibers, films or molded products,
! There is a high demand for materials with excellent 1111 properties, heat resistance, and chemical resistance. Polyester has come to be widely accepted for use in general molded products, but many polyesters have poor flexural modulus and bending strength, so high modulus and
It was not suitable for applications requiring high strength. In order to improve this mechanical property, it is known to blend reinforcing materials such as calcium carbonate and glass fiber, but this increases the specific gravity of the material, which reduces the light snacking benefits that plastics have. During molding, the molding machine is subject to severe wear and there are many practical problems.
補強材の必要がなく、高弾性率、高強度が要求される用
途に適しているポリエステルとして近年では液晶性ポリ
エステルが注目されるようになった。特に注目を集める
ようになったのは、ジャーナル・オブΦポリマー・サイ
エンス−ポリマー・ケミストリー・エディタヨン/参巻
(7976年)20≠3頁および特公昭r6−tfO/
6号公報にW、J、ジャクンンがポリエチレンテレフタ
レートとアセトキシ安息香酸とからなる熱液晶高分子を
発表してからである。この中でジャクソンは、この液晶
高分子がポリエチレンテレフタレートの5倍以上の剛性
、参倍以上の強度、2j倍以上の衝撃強度を発揮するこ
とを報告し、高機能性樹脂への新しい可能性を示した。In recent years, liquid crystalline polyester has attracted attention as a polyester that does not require a reinforcing material and is suitable for applications requiring high elastic modulus and high strength. The journals that have attracted particular attention are the Journal of Φ Polymer Science - Polymer Chemistry Editorial Edition (Vol. 7976) 20≠3 pages and the
This was after W, J, and Jakun published a thermal liquid crystal polymer composed of polyethylene terephthalate and acetoxybenzoic acid in Publication No. 6. In this work, Jackson reported that this liquid crystal polymer exhibited more than 5 times the stiffness, 3 times more strength, and 2j times more impact strength than polyethylene terephthalate, opening new possibilities for high-performance resins. Indicated.
一方我々は先に
一般式(A)
−C−R凰−G−0−R2−0−・・・・・・・・・(
A)〔式中R1は炭素数6〜2θの2価の芳香族炭化水
素基、炭素数弘〜二〇の2価の脂環式炭化水素基または
/および炭素数/〜弘θの2価の脂肪族基(但し芳香族
炭化水素基の芳香族環の水素原子はハロゲン原子、炭素
数/〜μのアルキルまたはアルコキシ基で置換されても
よい)を示し、R1は炭素数λ〜≠Qの2価の脂肪族炭
化水素、炭素数弘〜2Qの2価の脂環式炭化水素基、芳
香環を形成する炭素数が≦〜20であるコ価の芳香族炭
化水素基(但し芳香族炭化水素基の芳香環の水素原子は
ハロゲン原子、炭素数/〜lのアルキル基ま九はアルコ
キシ基で置換されてもよい)、または分子#10−/θ
θQのポリアルキレンオキシトコ価ラジカルを示す〕で
表わされる反復単位からなる原料オリゴエステルまたは
ポリエステルがこれらを構成する反復単位の量にしてS
〜デfモルチと一般式(B)HO−R3cooH・−−
−−−−−−(B)〔式中R3は芳香族炭化水素環を形
成する炭素数が6〜20であるコ価の芳香族基(但し芳
香族炭化水素基の水素原子はハロゲン原子、炭素数/〜
μのアルキル基またはアルコキシ基で置換されてもよい
〕で示されるヒドロキシカルボン酸を?!−jモルチを
反応させて共重合オリゴマーを作り(第1段IPf!
”)、次にアシル化剤を加えてアシル化を行ない(第2
段階)、さらに減圧下で重合を行なう(第3段階)3段
階からなる共重合ポリエステルの製造法を出願した(%
開昭≦0−/76!2j号、特開昭60−2弘!630
号)。On the other hand, we first prepared the general formula (A) -C-R凰-G-0-R2-0- (
A) [In the formula, R1 is a divalent aromatic hydrocarbon group having 6 to 2θ carbon atoms, a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms, or/and a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms. represents an aliphatic group (however, the hydrogen atom of the aromatic ring of the aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl or alkoxy group having carbon number/~μ), and R1 is a carbon number λ~≠Q divalent aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group having 1 to 2Q carbon atoms, covalent aromatic hydrocarbon group having ≦ to 20 carbon atoms forming an aromatic ring (however, aromatic The hydrogen atom of the aromatic ring of the hydrocarbon group may be substituted with a halogen atom, the alkyl group with carbon number/~l may be substituted with an alkoxy group), or molecule #10-/θ
The raw material oligoester or polyester consisting of repeating units represented by
~Def Morch and general formula (B) HO-R3cooH・--
-------(B) [In the formula, R3 is a covalent aromatic group having 6 to 20 carbon atoms forming an aromatic hydrocarbon ring (however, the hydrogen atom of the aromatic hydrocarbon group is a halogen atom, Number of carbons/~
A hydroxycarboxylic acid represented by [optionally substituted with an alkyl group or an alkoxy group]? ! -j molti is reacted to make a copolymerized oligomer (first stage IPf!
”), then add an acylating agent to perform acylation (second
We have filed an application for a method for producing copolymerized polyester, which consists of three steps: step) and further polymerization under reduced pressure (third step).
Kaisho≦0-/76!2j issue, Tokukaisho 60-2 Hiro! 630
issue).
又、重合の速度が速く、かつ昇華物を著しく少なくする
方法についても特願昭6O−207t1号において出願
済みであるが、このようにして製造した共重合ポリエス
テルは熱安定性において充分ではなかった。In addition, a method for increasing the polymerization rate and significantly reducing the amount of sublimate has been applied for in Japanese Patent Application No. 6O-207t1, but the copolyester produced in this way did not have sufficient thermal stability. .
そのような点を鑑み我々は鋭意検討した結果、熱安定性
の良好な共重合ポリエステルを製造する方法を見出した
。In view of these points, we conducted extensive research and found a method for producing a copolyester with good thermal stability.
即ち、本発明は前記3段階すなわち共重合オリゴマーを
作る第1段階、アシル化剤を加えてアシル化を行なう第
2段階、さらに減圧下で重合を行なう第3段階から成る
共重合ポリエステルの製造法において。That is, the present invention provides a method for producing a copolymerized polyester comprising the three steps described above, namely, the first step of producing a copolymerized oligomer, the second step of adding an acylating agent to perform acylation, and the third step of further polymerizing under reduced pressure. In.
第3段階の開始前までに、一般式(C)HOR40H・
・・・・・・・・(0)(式中R4は一般式(A)にお
けるR1と同義)で表わされるジヒドロキク化合物を添
加して、第3段階開始前において(A)のOR”O基1
00当量に対して
末端OH基当竜−末端C0OH基尚貴≧0尚量 ・・・
(1)(末端OH基及び末端C00H基はアシル化され
たものも含む)
になるようにして反応させることを特徴とする共重合ポ
リエステルの製造法、に存する。Before the start of the third stage, the general formula (C)HOR40H・
......(0) (wherein R4 has the same meaning as R1 in general formula (A)) is added to form the OR''O group of (A) before the start of the third step. 1
00 equivalent, terminal OH group - terminal C0OH group Naoki ≧ 0 equivalent ...
(1) (The terminal OH group and the terminal C00H group include acylated ones) A method for producing a copolymerized polyester, characterized by reacting in the following manner.
ここで末端OH基とは末端に存在するOH基とアシル化
された末端に存在するアシルオキ7基を意味し、それら
は
HO−R意〜、HO−R8〜、HOR4〜及びそれらの
アシルオキシ化されたものを意味する。Here, the terminal OH group means an OH group present at the terminal and an acyloxy group present at the acylated terminal, and these include HO-R~, HO-R8~, HOR4~ and their acyloxylated groups. It means something.
一方末端000H基とは末端に存在する0OOH基とア
シル化された末端に存在する酸無水物基(アシルエステ
ル)を意味し、それらは〜RICOOH1〜RaC00
H及ヒソレラノアシルエステル化されたものを意味する
。On the other hand, the terminal 000H group means the 0OOH group present at the terminal and the acid anhydride group (acyl ester) present at the acylated terminal, which are ~RICOOH1~RaC00
It means a compound that has been esterified with H and Hisorelanoacyl.
本発明をさらに詳細に貌、明する。 The present invention will now be described and explained in further detail.
従来法で製造し之共重合ポリエステルは第1段階で製造
したオリゴエステルの中に
−0−R2−0−R”−C−・・・・・・・・・(11
)(式中、R2およびR3は(A)および(B)式にお
けるR2およびR3と同義である)
で表わされるユニットが生成するため、末端基の一〇H
基と一000H基のバランスがくずれ、−0OOH基末
端が過剰になっている。そのため共重合体中にはOH基
以外にC0OH基がアシル化剤と反応して酸無水物結合
が生成したり、最終生成共重合ポリエステル中に末端カ
ルボン酸が残存していたりする念め、共重合ポリエステ
ルは熱に対して不安定になったものと考えられる。The copolymerized polyester produced by the conventional method contains -0-R2-0-R''-C- (11
) (wherein R2 and R3 have the same meanings as R2 and R3 in formulas (A) and (B)).
The balance between the group and the 1000H group is lost, and the -0OOH group end is in excess. Therefore, in addition to OH groups, C0OH groups in the copolymer may react with the acylating agent to form acid anhydride bonds, or terminal carboxylic acids may remain in the final copolymerized polyester. It is thought that the polymerized polyester has become unstable to heat.
そこで本発明においては過剰の一000H基に相当又は
それ以上の一般式(C)で表わされるジヒドロキシ化合
物を添加することにより過剰の−COOH基をなくし、
その後第λ段階のアシル化を行ない又はアシル化金行み
いつつジヒドロキシ化合物を添加し、減圧下型縮合反応
を行なうことにより熱安定性にすぐれる共重合ポリエス
テルを製造することが可能となつ念。Therefore, in the present invention, the excess -COOH group is eliminated by adding a dihydroxy compound represented by the general formula (C) equivalent to or more than 1000H groups,
After that, it is possible to produce a copolymerized polyester with excellent thermal stability by carrying out the λ-stage acylation or adding a dihydroxy compound while performing the acylation, and carrying out a condensation reaction under reduced pressure.
本発明は一般式(A)で表わされるポリエステルまたは
オリゴエステルとオキシカルボン駿ヲ反応させて共重合
オリゴマーにした後にアシル化しさらに減圧下で重合す
るととくよシ実施される。さらに詳細に説明すると一般
式(A)で表わされるポリエステルteはオリゴエステ
ルを製造するためKは一般式(E)で表わされるジカル
ボン酸
aoocRlcoam −−−−−−−
−−(E)(式中、R1は一般式(A)におけると同義
)オヨびそのエステルが使用されるがカルボン酸の例を
示すとテレフタル酸、メトキシテレフタル醍、エトキ7
テレフタル酸、フルオロテレフタル酸、クロロテレフタ
ル酸、メチルテレフタル酸、イソフタル酸、7タル酸、
メトキシイソフタルH、ジフェニルメタン≠、r−ジカ
ルボン醗、ジフェニルメタン3,31−ジカルボン酸、
ジフェニルエーテル弘、≠′−ジカルボン酸、ジフェニ
ル−札y′−ジカルボン酸、ナフタリン−,21g−ジ
カルボン酸、ナフタリン/、、!ジカルボン酸、ナフタ
リン1,4ジカルボン酸、アジピン酸、セパシン酸、ア
ゼライン酸、スペリン酸、ドデカンジカルボン酸、3−
メチルアゼライン酸、グリタール酸、コハク酸、シクロ
ヘキサン1,4ジカルボン酸、ククロヘキサン/、3ジ
カルボン酸、シクロベ/タン/、!ジカルボン酸などが
挙げられる。これらは混合して使用してもよく一般式(
K)で表わされるものはいずれも使用可能である。The present invention is particularly carried out by reacting the polyester or oligoester represented by the general formula (A) with oxycarbon to form a copolymerized oligomer, followed by acylation and further polymerization under reduced pressure. To explain in more detail, the polyester te represented by the general formula (A) is used to produce an oligoester, so K is the dicarboxylic acid aoocRlcoam represented by the general formula (E).
--(E) (In the formula, R1 has the same meaning as in general formula (A)) Oyobis ester is used, but examples of carboxylic acids include terephthalic acid, methoxyterephthalate, ethyl 7
Terephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, methylterephthalic acid, isophthalic acid, heptalic acid,
Methoxyisophthal H, diphenylmethane≠, r-dicarboxylic acid, diphenylmethane 3,31-dicarboxylic acid,
Diphenyl ether, ≠'-dicarboxylic acid, diphenyl-dicarboxylic acid, naphthalene, 21g-dicarboxylic acid, naphthalene/,! Dicarboxylic acid, naphthalene 1,4 dicarboxylic acid, adipic acid, sepacic acid, azelaic acid, speric acid, dodecanedicarboxylic acid, 3-
Methyl azelaic acid, glitaric acid, succinic acid, cyclohexane 1,4 dicarboxylic acid, cuclohexane/, 3 dicarboxylic acid, cyclobe/than/,! Examples include dicarboxylic acids. These may be used in combination with the general formula (
K) can be used.
また一般式(A)を型造する念めに使用される一般式(
F)で表わされるジオール
HOR”OR−・山川−(F)
(式中、HNは一般式(A)におけると同義)の具体例
としてはエチレングリコール、/、3−プロパンジオー
ル、/、2−プロパンジオール、/、3−ブタンジオー
ル% /、41.−ブタンジオール、ネオペンチルグリ
コール、/、6ヘキサンジオール、/μココ−デカンジ
オール、シクロヘキサン/、41−ジオール、シクロヘ
キサンl、3ジオール、シクロヘキサン/、2−ジオー
ル、シクロベンペンタン!、!−ジオール、ジエチレン
クリコール、ポリエチレングリコール、ヒドロキノン、
レゾルシノール、ビスフェノールA1メチルヒドロキノ
ン、クロルヒドロキノン、コツ6−ナフタリンジオール
などが挙げられるが、これらは混合して使用してもよく
、一般式(F)で表わされるものはいずれも使用可能で
ある。In addition, the general formula (
Specific examples of the diol HOR"OR-・Yamakawa-(F) (in the formula, HN has the same meaning as in general formula (A)) represented by F) include ethylene glycol, /, 3-propanediol, /, 2- Propanediol, /, 3-butanediol% /, 41.-Butanediol, neopentyl glycol, /, 6hexanediol, /μ coco-decanediol, cyclohexane/, 41-diol, cyclohexane l, 3diol, cyclohexane/ , 2-diol, cyclobenpentane!, !-diol, diethylene glycol, polyethylene glycol, hydroquinone,
Examples include resorcinol, bisphenol A1 methylhydroquinone, chlorohydroquinone, and 6-naphthalene diol, but these may be used in combination, and any of those represented by general formula (F) can be used.
本発明で用いる式(A)で示されるポリエステルま九は
オリゴエステルとしては一般式(A)で表わされるもの
はいずれも使用可能であるがその入手のしやすさからポ
リエチレンテレフタレート、ポリブチレンテレフタレー
トおよびそれらのオリゴマーが好ましく、特にポリエチ
レンテレフタレートおよびそのオリゴマーが好ましい。Regarding the polyester represented by the formula (A) used in the present invention, any oligoester represented by the general formula (A) can be used, but polyethylene terephthalate, polybutylene terephthalate and Those oligomers are preferred, especially polyethylene terephthalate and its oligomers.
式(B)のヒドロキシカルボン酸としてはバラヒドロキ
シ安息香酸、≠−ヒドロキシ3−クロロ安息香酸、メタ
ヒドロキシ安息香酸、≠−ヒドロキシJ、j−ジメチル
安息香酸、コーオキシ乙−ナフトエ酸、!−オキシj−
ナフトエ酸、/−ヒドロキシ−弘−ナフトエ酸、シュリ
ンガ−酸、バニリン酸、弘−ヒドロキシ−3−メチル安
息香酸などが挙げられる。バラヒドロキシ安息香#を単
独で用いるのが溶融異方性を保つためには好ましいが一
般式(B)で表わされるヒドロキシカルボン酸はいずれ
も使用可能であるしまたこれらを混合して使用してもか
まわない。Examples of the hydroxycarboxylic acid of formula (B) include parahydroxybenzoic acid, ≠-hydroxy 3-chlorobenzoic acid, metahydroxybenzoic acid, ≠-hydroxy J, j-dimethylbenzoic acid, cooxy-naphthoic acid, and! -oxyj-
Examples include naphthoic acid, /-hydroxy-hiro-naphthoic acid, Schlinger's acid, vanillic acid, and hiro-hydroxy-3-methylbenzoic acid. Although it is preferable to use rose hydroxybenzoic acid # alone in order to maintain melt anisotropy, any hydroxycarboxylic acid represented by the general formula (B) can be used, or a mixture of these can be used. I don't mind.
また(B)のヒドロキシカルボン酸と一般式(A)で表
わされるポリエステルとオリゴエステルとの反応は20
0〜350℃、好ましくは220〜3Qθ℃で行なわれ
、反応は!分〜/θ時間、好ましくは20分〜!時間の
節回で行なわれる。In addition, the reaction between the hydroxycarboxylic acid (B), the polyester represented by the general formula (A), and the oligoester is 20
The reaction is carried out at 0 to 350°C, preferably 220 to 3Qθ°C! minutes ~/θ hours, preferably 20 minutes ~! It is done in a timely manner.
反応は、ヒドロキシカルボン酸化合物の残存量が仕込量
に対し、通常70モルチ以下、好ましくは!θモルチ以
下、特に好ましくは4LOモルチ以下となるまでおこな
われる。In the reaction, the residual amount of the hydroxycarboxylic acid compound is usually 70 mole or less based on the amount charged, preferably! This is carried out until it reaches θ molti or less, particularly preferably 4LO molti or less.
!た反応は無触媒でも可能であるが必要に応じ、触媒を
添加して実施される。! Although the above reaction can be carried out without a catalyst, it can be carried out with the addition of a catalyst if necessary.
本発明で使用される(C)のジヒドロキシ化合物として
は一般式(0)で表わされるものがいずれも使用出来る
が、具体例としてはハイドロキノン、レゾルシン、メチ
ルハイドロキノン、クロロハイドロキノン、t−ブチル
ハイドロキノン、2.jジt−ブチルハイドロキノン、
コ、弘、イトリメチルレゾルシン、ナフトハイドロキノ
ン、≠、μ′ビフェノール、アセトキシハイドロキノン
、ニトロハイドロキノン、ジメチルアミノハイドロキノ
ン、1,4−ジヒドロキ7ナフトール、/、j−ジヒド
ロキシナフトール、/、6−ジヒドロキシナフトール、
コ、≦−ジヒドロキシナフトール、コ、7−シヒドロキ
クナ7トール、2.2’−ビス(弘−ヒドロキシフェニ
ル)フロパン、2.2′−ビス(4t−−ヒドロキシ−
J、s−ジメチルフェニル)フロパン1.2.2’−ビ
ス(仙−ヒトロキシ3.j−ジクロロフェニル)−プロ
パン、2.2′−ビス(≠−ヒドロキクー3−メチルフ
ェニル)−プロパン、2.2′−ビス(4L−ヒドロキ
シ−3−クロロフェニル)プロパン、ビス(弘−ヒドロ
キシフェニル)−メタン、ビス(4A−ヒドロキシ−3
,5−ジメチルフェニル)−メタン、ビス(4=−ヒド
ロキク−3,j−ジクロロフェニル)−メタ/、ビス(
I/−−ヒドロキシ−3、j−ジブロモフェニル)−メ
タン、/、/−ビス(4t−ヒドロキシフェニル)シク
ロヘキサン、tx、、4!、’−ジヒドロキシジフェニ
ルビス(≠−ヒドロキシフェニル)−ケトン、ビス(≠
−ヒドロキシー3.!−ジメチルフェニル)−ケトン、
ビス(弘−ヒドロキシ−3,J−−ジクロロフェニル)
−ケトン、ビス(≠−ヒドロキシフェニル)スルフィド
、ビス(4−ヒドロキシ−3−クロロフェニル)スルフ
ィド、ビス(4t−ヒドロキシフェニル)スルホン、ビ
ス(4L−ヒドロキシ−3、s −ジクロロフェニル)
エーテル、等カ挙ケられる。As the dihydroxy compound (C) used in the present invention, any compound represented by the general formula (0) can be used, but specific examples include hydroquinone, resorcinol, methylhydroquinone, chlorohydroquinone, t-butylhydroquinone, .. j di-t-butylhydroquinone,
Ko, Hiroshi, itrimethylresorcinol, naphthohydroquinone, ≠, μ′ biphenol, acetoxyhydroquinone, nitrohydroquinone, dimethylaminohydroquinone, 1,4-dihydroxnaphthol, /, j-dihydroxynaphthol, /, 6-dihydroxynaphthol,
Co, ≦-dihydroxynaphthol, Co, 7-dihydroquiknaphthol, 2,2'-bis(Hiro-hydroxyphenyl)furopane, 2,2'-bis(4t-hydroxy-
J, s-dimethylphenyl)furopane 1.2.2'-bis(sen-hydroxy3.j-dichlorophenyl)-propane, 2.2'-bis(≠-hydroxy-3-methylphenyl)-propane, 2.2 '-Bis(4L-hydroxy-3-chlorophenyl)propane, bis(Hiro-hydroxyphenyl)-methane, bis(4A-hydroxy-3
,5-dimethylphenyl)-methane, bis(4=-hydroxy-3,j-dichlorophenyl)-meta/, bis(
I/--hydroxy-3,j-dibromophenyl)-methane, /,/-bis(4t-hydroxyphenyl)cyclohexane, tx,,4! ,'-dihydroxydiphenylbis(≠-hydroxyphenyl)-ketone, bis(≠
-Hydroxy 3. ! -dimethylphenyl)-ketone,
Bis(Hiro-hydroxy-3,J--dichlorophenyl)
-ketone, bis(≠-hydroxyphenyl) sulfide, bis(4-hydroxy-3-chlorophenyl) sulfide, bis(4t-hydroxyphenyl)sulfone, bis(4L-hydroxy-3,s-dichlorophenyl)
Ether, etc. are mentioned.
一般式(C)で表わされる化合物の添加は第3段階の開
始前であればいつでもよいが、特に第1段階の反応の終
了後に加えるのが好ましい。The compound represented by the general formula (C) may be added at any time before the start of the third stage, but it is particularly preferably added after the first stage reaction is completed.
一般式(0)で表わされる化合物の量は、第3段階開始
前の反応混合物中、(A)のoRt O残基/θ0当令
に対して
(1)末端OH基当量−末端000F1基当量≧0尚量
(末端OH基、末端C0OH基はアシル化され九ものも
含む)、好ましくは(i)がj当葉以上弘O当量以下に
なるように添加することが好ましい。The amount of the compound represented by the general formula (0) in the reaction mixture before the start of the third step is (1) terminal OH group equivalent - terminal 000F1 group equivalent relative to oRtO residue/θ0 equivalent of (A) ≧0 equivalents (the terminal OH group and the terminal COOH group are acylated, including nine), preferably in such a manner that (i) is equal to or more than J equivalent and equal to or less than HiroO equivalent.
参〇轟量を超えると熱安定性は良いが重合速度が遅くな
る九め好ましくない。If the amount exceeds 100%, the thermal stability is good, but the polymerization rate slows down, which is undesirable.
末端基の量は第3段階開始時の反応液を分析するととK
よシアらかじめ把握することは可能である。The amount of terminal groups can be determined by analyzing the reaction solution at the start of the third step.
It is possible to understand this in advance.
末端基はE−NMRを用い、DMSO等の溶媒中で測定
可能でおる。The terminal group can be measured using E-NMR in a solvent such as DMSO.
例えば
*
ho o c o o 〜 の*のプロトンは6.t
r j ppm*
HO(H,aFizO〜 の*のプロトンはへ
02 ppm酸についてはメチルエステル化することに
より等を用いて必要か末端基の濃度を求めることが可能
である。For example, the * proton in * ho o c o o ~ is 6. t
r j ppm* HO (H, aFizO~ The * proton of 02 ppm acid can be used to determine the concentration of the necessary terminal group by methyl esterification, etc.).
一方、使用される(A)の末端基の測定及び生成する(
D) −0−R2−0−R3−C!−の測定から末端末
端OH基−末端GOOH基〈0当量の場合はロキシ化合
物を添加することは重合速度の低下、昇華の発生など悪
影響があフ好ましくない。On the other hand, measurement of the terminal group of (A) used and generation (
D) -0-R2-0-R3-C! - From the measurement of terminal terminal OH group - terminal GOOH group (0 equivalent), it is not preferable to add a roxy compound because it has adverse effects such as a decrease in the polymerization rate and the occurrence of sublimation.
添加方法としてはバルクで添加してもよいし、希釈剤を
用いて希釈して添加してもよい。As for the addition method, it may be added in bulk, or it may be diluted with a diluent and added.
又、(C)を二種以上用いることも物性をコントロール
できるという点で好ましい。例えば液晶性を高めるハイ
ドロキノンや弘J′−ビスフェノールと液晶性を低下す
るレゾルシンやコ、2′−ビス(≠−ヒドロキシフェニ
ル)フロハ:/ 等e組合わせると、原料の(A)や(
B)の組成を変化させることなく所望の物性値にするこ
とが可能である。It is also preferable to use two or more types of (C) in that the physical properties can be controlled. For example, when combined with hydroquinone and Hiroj'-bisphenol, which increase liquid crystallinity, and resorcinol, co-, and 2'-bis(≠-hydroxyphenyl)fluorocarbons, which reduce liquid crystallinity, the raw materials (A) and (
It is possible to obtain desired physical property values without changing the composition of B).
(C)の添加′!には前記条件を達成するように選ばれ
れば特に制限はないが、通常、(B)の量の/〜!Qモ
ルチである。Addition of (C)'! There is no particular restriction on the amount of (B) as long as it is selected to meet the above conditions, but usually the amount of /~! This is Q Morchi.
第二段階であるアシル化はアシル化剤を(アシル化剤)
/((B) +2 (C) )でQ、5倍モル以上、2
90倍モル以下、好ましくは0.7倍モル以上/、j倍
モル以下使用して行われ、その場合のアシル化剤の滴下
時間は自由であるが、望ましくは70分以上、好ましく
は20分以上で実施される。アシル化剤との接触は20
℃〜3丁θ℃で行われるが好ましくは!θ℃〜200℃
、より好寸しくはrθ℃ヘー//θ℃で行われ、加圧に
してもよい。The second step, acylation, uses an acylating agent (acylating agent).
/((B) +2 (C) ), Q, 5 times the mole or more, 2
It is carried out using 90 times the mole or less, preferably 0.7 times the mole or more/j times the mole or less, and in that case, the dropping time of the acylating agent is arbitrary, but desirably 70 minutes or more, preferably 20 minutes. The above will be implemented. Contact with acylating agent is 20
It is preferably carried out at a temperature of ℃ to 3 θ℃! θ℃〜200℃
, more preferably at rθ°C//θ°C, and may be under pressure.
又、系をアシル化剤の沸点以下まで下げてアシル化を行
なってもよい。反応は5時間以内、好ましくは10分以
上〜3時間の範囲で行なわれる。Alternatively, acylation may be carried out by lowering the temperature of the system to a temperature below the boiling point of the acylating agent. The reaction is carried out within 5 hours, preferably in the range of 10 minutes or more to 3 hours.
このアシル化の終了までに一般式(C)のジオールを添
加しておけばよい。The diol of general formula (C) may be added before this acylation is completed.
またアシル化剤としては無水酢酸、無水プロピオン酸、
無水酪酸、無水安息香酸などが使用されるがアシル化剤
として一般に使用可能なものはいずれも使用可能であり
、それらの中で反応性およびコストの面から無水酢酸が
代表的なものである。In addition, acylating agents include acetic anhydride, propionic anhydride,
Although butyric anhydride, benzoic anhydride, etc. are used, any commonly usable acylating agent can be used, and among them, acetic anhydride is representative from the viewpoint of reactivity and cost.
次に第三段階の重合ld、200℃〜3JO′C。Next, the third stage of polymerization ld, 200°C to 3JO'C.
好ましくは2.20℃〜330℃で実施されるが、この
場合初期に徐々に減圧にすることが好ましく%760r
ttxHyから/mHyiで徐々に減圧にする場合に要
する時間rd3o分以上、好ましくは60分以上の時間
で実施され、特に/θwnHy1分から/ [Hy 7
分の減圧を徐々に行なうことが重要である。It is preferably carried out at a temperature of 2.20°C to 330°C, but in this case it is preferable to gradually reduce the pressure at an initial temperature of 760r
The time required to gradually reduce the pressure from ttxHy to /mHyi is rd3o minutes or more, preferably 60 minutes or more, especially from /θwnHy1 minute/ [Hy 7
It is important to perform the depressurization gradually.
第二段階および第三段階においても無触媒でも可能であ
るが必要に応じ触媒の存在下で実施される。The second and third stages can also be carried out without a catalyst, but may be carried out in the presence of a catalyst if necessary.
第一段階、第二段階および第三段階で使用される触媒と
してはエステル交換触媒、重縮合触媒、アシル化触媒、
脱カルボン酸触媒が使用され、これらは混合して使用し
てもかまわない。Catalysts used in the first, second and third stages include transesterification catalysts, polycondensation catalysts, acylation catalysts,
Decarboxylation catalysts are used, and these may be used in mixtures.
その使用量はポリマーに対して!〜!θ、000ppm
好ましくはj O〜j 000 ppmである。The amount used is relative to the polymer! ~! θ, 000ppm
Preferably it is j O to j 000 ppm.
またηinhはフェノールとテトラクロロエタ/を以上
、好ましくは0.J ! dt/ を以上である。In addition, ηinh is phenol and tetrachloroethane/ or more, preferably 0. J! dt/ is above.
このようにして製造された共重合ポリエステルは末端C
0OH基よりも末端−OH基及びそのアシルオキシ基の
方の数が多いため、耐熱水性、耐加水分解性にすぐれる
という長所を有する。The copolymerized polyester thus produced has a terminal C
Since there are more terminal -OH groups and their acyloxy groups than 0OH groups, it has the advantage of excellent hot water resistance and hydrolysis resistance.
以下に実施例により本発明を具体的に説明するが本発明
はその要旨fI:越えない限υ以下の実施例に限定され
るものではない。The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples.
実施例/
攪拌翼、窒素導入口、減圧口を備えたガラス重合管にp
−ヒドロキシ安息香酸! /、J” ?(0,371モ
ル)、ポリエチレンテレ7タレートオリゴーr −(η
1nh= 0.09Fdt/ f ) 72./2(反
覆単位の量として0.37jモル)、酢酸第一スズ0,
037 tを仕込み、減圧−窒素置換を3回繰り返し、
最後に窒素を満たし、θ、j 1.7Mの流量の窒素気
流下におく。重合管を24Lθ℃のオイルバスに浸漬す
ると30分程で内容物が溶融するので、攪拌を開始し、
そのままコ時間エステル交換を行ない共重合オリゴマー
を作る。Example/ A glass polymerization tube equipped with a stirring blade, a nitrogen inlet, and a pressure reduction port was
-Hydroxybenzoic acid! /, J”? (0,371 mol), polyethylene tere-7-thalerate oligor −(η
1nh=0.09Fdt/f) 72. /2 (0.37 j mol as repeating unit amount), stannous acetate 0,
037t was charged, vacuum and nitrogen substitution was repeated three times,
Finally, it is filled with nitrogen and placed under a nitrogen flow with a flow rate of θ,j of 1.7M. When the polymerization tube is immersed in an oil bath at 24Lθ℃, the contents will melt in about 30 minutes, so start stirring,
A copolymerized oligomer is produced by performing co-transesterification as it is.
その後/≠Q′Cまで3Q分程で降温し、ハイドロキノ
ンf?、25?(0,075モル)添加し、次に無水酢
酸57?(07≦57モル)を3o分かけて滴下し、千
の′ままさらに7時間攪拌を続はアシル化を行なう。そ
の後オイルバスの温度を273T:、まで2時間かけて
昇温し、酢酸亜鉛二水和物θ、Oj ? tを加え、徐
々に減圧を適用する。そしてOi mm Hyの高真空
になってから3時吋重合を行なう。生成物はガラス重合
管を割って取り出しチップ化した後/3θ℃で一晩X空
乾燥する。得られ念ポリマーは乳白色不透明でありηi
nh =0.70であつ之。After that, the temperature dropped in about 3Q minutes to /≠Q'C, and the hydroquinone f? , 25? (0,075 mol) and then acetic anhydride 57? (07≦57 mol) was added dropwise over 30 minutes, and the mixture was stirred for a further 7 hours, followed by acylation. After that, the temperature of the oil bath was raised to 273T:, over 2 hours, and zinc acetate dihydrate θ, Oj ? t and gradually apply vacuum. Then, after reaching a high vacuum of Oi mm Hy, polymerization was carried out for 3 hours. The product was taken out by breaking the glass polymerization tube and made into chips, and then air-dried overnight at 3θ°C. The obtained polymer is milky white and opaque, and ηi
nh = 0.70.
このポリマーをさらに120℃でオープン乾燥を130
時間行なってもηinh = 0゜7Qと熱安定性にす
ぐれるものであった。This polymer was further open-dried at 120°C for 130°C.
The thermal stability was excellent, with ηinh = 0°7Q even after repeated tests.
又工Rの結果より酸無水物結合は全くなかった。Also, the results of Engineering R showed that there was no acid anhydride bond at all.
この系ではNMR解析により第3段階開始前までに10
0当量の一〇〇)(富CI’!、O−基に対して末端O
H基 !7.6当量
末端C0OH基 J O,!当量
(いずれもアセチル化された基も含む)であり
末端OH基−末端COOH基=26゜r当量であり九。In this system, NMR analysis shows that 10
0 equivalent 100) (rich CI'!, terminal O to O- group
H group! 7.6 equivalent terminal C0OH group J O,! Equivalent (all including acetylated groups), terminal OH group - terminal COOH group = 26°r equivalent, 9.
又、仕込ポリエチレンテレフタレートオリゴマーの末端
OH基は/θθ当量の一00H,OH,O−基に対し2
0当量あり、
末端C0OH基は72当量、生成エーテル成分は700
当量の一0CR,CH20−基に対して//当量であり
添加したハイドロキノンの01’I基は/θθ当景当量
0CR1CH20−基に対して≠θ当伺゛あるので第3
段階開始前までの
末端OR基−末端Coo:FI基は
(2o−(//X2 )十弘θ)−/2=26 とな
り上記の結果と一致した。In addition, the terminal OH group of the charged polyethylene terephthalate oligomer is 2 per 100H, OH, O- group of /θθ equivalent.
There are 0 equivalents, the terminal C0OH group is 72 equivalents, and the generated ether component is 700
The 01'I group of the added hydroquinone is // equivalent to the equivalent 10CR, CH20- group, and the 01'I group of the added hydroquinone is ≠θ equivalent to the /θθ equivalent 0CR1CH20- group, so the third
The terminal OR group-terminal Coo:FI group before the start of the step was (2o-(//X2) Tohiro θ)-/2=26, which was consistent with the above result.
この生成共重合ポリエステルの末端は
ポリエステル/、062あたり
OH末端基は実質上 O当量
o c OH,末端基は /2を当量
C!OOE末端基は ≦6当量
であり共重合ポリエステルの末端はOII基(アセチル
化されたものを含む)リッチであった。The terminals of this copolymerized polyester are polyester/, 062, and the OH terminal groups are substantially O equivalent o c OH, and the terminal groups are /2 equivalent to C! The OOE end groups were ≦6 equivalents, and the ends of the copolyester were rich in OII groups (including acetylated ones).
実施例コ
攪PR%窒素導入ロ、減圧口を備えたガラス重合管にp
−ヒドロキシ安息香酸62,2 f (0,41jモル
)ポリエチレンテレフタレートオリゴマー(ηinh
= 0,0り/ dl/l ) j 7,7 f (0
,30モ/L/)酢酸第一スズθ、θJtfを仕込み、
減圧−窒素置換を3回繰り返し、最後に窒素を滴たし、
0、j1/11riRの流量の窒素気流下におく。重合
管を2/、O’Cのオイルバスに浸漬すると30分程で
内容物が溶融するので攪拌を開始し、そのまt2時間エ
ステル交換を行ない共重合オリコ′マーを作る。その後
、ノーイドロキノンを/、、2 ! S’(0゜075
モル)添加し、次に無水酢酸/22.弘f1f:J 0
分かけて滴下し、その−1まさらに7時間攪拌を続け、
アシル化を行なう。その後オイルバスの温度をJ7j’
Cまで1時間かけて昇温し、酢酸亜鉛二水和物0.04
/ tを加え、徐々に減圧を適用する。そしてθ、J
ttxHfの高真空になってから2時間重合を行なった
。得られたポリマーのηinh = 0./ 7であっ
た。このポリi−をさらに720℃でオープン乾燥f、
/30時間行なってもηinh = 0.1” jと熱
安定性にすぐれるものであった。Example Co. Stir PR% Nitrogen introduction b, p into a glass polymerization tube equipped with a decompression port
-Hydroxybenzoic acid 62,2 f (0,41 j mol) Polyethylene terephthalate oligomer (ηinh
= 0,0ri/dl/l) j 7,7 f (0
, 30 mo/L/) stannous acetate θ, θJtf,
Repeat depressurization and nitrogen substitution three times, and finally add nitrogen dropwise.
Place under nitrogen flow at a flow rate of 0,j1/11riR. When the polymerization tube is immersed in a 2/O'C oil bath, the contents will melt in about 30 minutes, so stirring is started and transesterification is carried out for 2 hours to produce a copolymerized oligomer. After that, take noidoquinone/,,2! S'(0°075
mol) and then acetic anhydride/22. Hirof1f: J 0
Add it dropwise over a few minutes and continue stirring for another 7 hours.
Perform acylation. Then set the temperature of the oil bath to J7j'
The temperature was raised to C over 1 hour, and zinc acetate dihydrate 0.04
/t and gradually apply vacuum. and θ, J
Polymerization was carried out for 2 hours after the high vacuum of ttxHf was established. ηinh of the obtained polymer = 0. / It was 7. This poly i- is further open-dried at 720°C,
Even after 30 hours, ηinh = 0.1''j, showing excellent thermal stability.
工Rの結果より酸無水物結合は全くなかつ念。From the results of Engineering R, we are confident that there is no acid anhydride bond at all.
この系ではNMR解析の結果、第3段階開始前までに1
00当量の一00H,C1(、O−基に対して末端OH
基 J /、44当量
末端CooH基 32゜j当量
(いずれもアセチル化された基も含む)であシ
末端OH基−末端C0OH基=j、?当量であった。In this system, as a result of NMR analysis, 1
00 equivalent of 100H, C1 (, terminal OH to O- group
Group J /, 44 equivalents Terminal CooH group 32゜j equivalents (all including acetylated groups) Terminal OH group - Terminal C0OH group = j, ? The amount was equivalent.
又仕込ポリエチレンテレフタレートオリゴマーの末端O
H基、末端C!OOH基、生成エーテル成分及びハイド
ロキノンは700当量の一〇CI(1CH20−基に対
してそれぞれ20当量、/2当量、26当量及び−25
当景であるので第3段階開始前までの
末端OH基−末端000H基は
〔コθ−(2≦X2)+(コ5x2))−/J=4とな
υ上の結果と一致した。Also, the terminal O of the charged polyethylene terephthalate oligomer
H group, terminal C! The OOH group, the generated ether component, and the hydroquinone were 700 equivalents of 10 CI (20 equivalents, /2 equivalents, 26 equivalents, and -25 equivalents, respectively, per 1 CH20- group).
Since this is the current situation, the terminal OH group-terminal 000H group before the start of the third stage is [θ-(2≦X2)+(KO5×2))−/J=4, which is consistent with the result on υ.
比較例/
ハイドロキノンを加えることを除いては実施例コと全く
同一のことを行なった。Comparative Example: The same procedure as in Example 1 was carried out except that hydroquinone was added.
生成ポリマーのηinh =0.7/であった。ηinh of the produced polymer was 0.7/.
ところがこのポリマーを120℃オーブン乾燥を72時
間行なったところηinh = 0.j jと大幅に低
下した。However, when this polymer was oven dried at 120°C for 72 hours, ηinh = 0. j j and decreased significantly.
1只の結果より酸無水物結合はエステル結合に対し約/
Q%存在してい九。From the results of 1, the acid anhydride bond is approximately /
Q% exists.9.
この場合第3段階開始前までの
OH基−〇〇〇FK基= (,2a−(、zgx2))
−t2=−+弘〈Qであった。In this case, OH group-〇〇〇FK group before the start of the third stage = (,2a-(,zgx2))
-t2=-+Hiroshi〈Q.
実施例3
実施例/のハイドロキノン?、2 Jr tのかわりに
ハイドロキノン≠、/λ!fルゾルシン弘、/ j J
”tを用いた以外は実施例/と同様に行った。Example 3 Hydroquinone of Example/? , 2 Jr t instead of hydroquinone ≠, /λ! f Hiroshi Ruzorsin, / j J
The same procedure as in Example 1 was carried out except that "t" was used.
得られ九ポリマーのηinh =0.60であり、/2
θ℃2=ブン乾燥730時間後でもη1nh= 0.s
9であった。ηinh of the nine polymers obtained = 0.60, /2
θ℃2= Even after 730 hours of bun drying, η1nh=0. s
It was 9.
又IRの結果よシ酸無水物結合は全くなかつた。Moreover, the IR results showed that there was no sialic acid anhydride bond at all.
末端OH基と末端000H基の差(当量)は実施例/と
同じであった。The difference (equivalent) between the terminal OH group and the terminal 000H group was the same as in Example.
比較例2
ハイドロキノン*t0.03θモル添加する以外は実施
例コと同様に行なった。Comparative Example 2 The same procedure as in Example 2 was carried out except that 0.03θ mole of hydroquinone*t was added.
得られ念ポリマーはηinh = 0゜7Sであったが
酸無水物結合がエステル結合に対し約へ5%存在してい
た。/−0℃のオーブン乾燥を730時間行なうとr!
inh = o、≦7と低下した。The resulting polymer had ηinh = 0°7S, and acid anhydride bonds existed in an amount of about 5% relative to ester bonds. / After 730 hours of oven drying at -0°C, r!
inh = o, decreased to ≦7.
この場合ioo轟量の一00H!OH,O−基に対して
原料の末端OI(基は20当量、末端ccioa基は/
2当量、エーテル結合は2≦轟量存在するので
OH基−000H基=(2θ−(2ご×2)+(10×
コ))−/、2=−2弘〈θ となる。In this case, ioo 100H! The terminal OI of the raw material with respect to the OH, O- group (the group is 20 equivalents, the terminal ccioa group is /
2 equivalents, and since there are 2≦amounts of ether bonds, OH group - 000H group = (2θ - (2 x 2) + (10 x
ko))-/, 2=-2hiro〈θ.
実施例≠
ポリエチレンテレフタレートオリゴマーを2 r、t
? (0,t 、rモル)、p−ヒドロキシ安息香酸r
、2tt<0.50モル)ヲ用い、ハイドロキノンを弘
、t3t(θ、(7j 7 jモル)添加し、無水酢酸
量を!≠、2 f (0,? 3モル)添加し九以外は
実施例/と同様に行なった。Example ≠ Polyethylene terephthalate oligomer 2 r, t
? (0,t, r mol), p-hydroxybenzoic acid r
, 2tt < 0.50 mol), hydroquinone was added at t3t (θ, (7j 7 j mol), and the amount of acetic anhydride was added!≠, 2 f (0,? 3 mol). All steps except 9 were carried out. It was done in the same way as Example/.
得られたポリマーのηinh = 0.9 /であった
。The obtained polymer had ηinh=0.9/.
工RGCより酸無水物結合は認められなかった。No acid anhydride bond was observed by RGC.
10θ当量の−QC!H,CIII、O−基に対してポ
リエステルオリゴマーの末端OH基コθ当量、末端co
on基72基量2当量テル成分はコ!轟量であるので
末端OR基−末端C0OH基=
(so−(2,、rxx)+ (、zjxz)’j−y
x=+r当量であった。-QC of 10θ equivalent! H, CIII, terminal OH group co θ equivalent of polyester oligomer with respect to O- group, terminal co
On group 72 base weight 2 equivalent Ter component is ko! Since the amount is large, terminal OR group - terminal C0OH group = (so-(2,, rxx) + (, zjxz)'j-y
x=+r equivalent.
実施例!
原料としてポリエステルポリマー(ηinh =0.6
/ ) ft用い、第1段階のオリゴマーを作る温度
を270℃添加するハイドロキノンを/r、/ry (
0,t≦5モル)添加し、無水酢酸を79.2t(0,
776モル)を加える以外は実施例/と同様に行った。Example! Polyester polymer (ηinh = 0.6
/ ) ft, add hydroquinone at a temperature of 270°C to make the first stage oligomer /r, /ry (
79.2t (0.0,t≦5mol) of acetic anhydride was added.
The same procedure as in Example 1 was carried out except that 776 mol) was added.
得られたポリマーはηinh =θ、7コであり、この
ポリマーをさらに720℃でオーブン乾燥を730時間
行ってもηinh = 0.72と熱安定性にすぐれる
ものであった。The obtained polymer had ηinh = θ, 7, and even when this polymer was further dried in an oven at 720° C. for 730 hours, it had excellent thermal stability with ηinh = 0.72.
又、工Rの結果より酸無水物結合は全くなかった。Furthermore, the results of Engineering R showed that there was no acid anhydride bond at all.
この系ではNMR解析により第3段階開始前までに70
θ当景の一0CR,CH,O−基に対して末端OH基
1I−3゜2当食
末端C0OH基 22.3当量
(いずれもアセチル化された基も含む)であり
末端OH基−末端000H基=λへ≠当量であった、
実施例6
ハイドロキノンを最初から添加したこと以外は実施例/
と同様に行った。In this system, NMR analysis shows that 70
θThe terminal OH group for one 0CR, CH, O- group in the current view
1I-3゜2 The terminal C0OH group at 22.3 equivalents (all including acetylated groups), and terminal OH group - terminal 000H group = ≠ equivalent to λ. Example 6 Hydroquinone was prepared from the beginning. Example/ except for the addition of
I did the same thing.
得られたポリマーはηinh = 0.72であった。The obtained polymer had ηinh=0.72.
末端OH基と末端CooH基の差(当量)は実施例/と
同じであった。The difference (equivalent) between the terminal OH group and the terminal CooH group was the same as in Example.
以上のように水層発明方法によると、熱安定性のすぐれ
た共重合ポリエステルが得られるものである。As described above, according to the water layer invention method, a copolymerized polyester having excellent thermal stability can be obtained.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 −ほか/名Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/Names
Claims (7)
基、炭素数4〜20の2価の脂環式炭化水素基または/
および炭素数1〜40の2価の脂肪族炭化水素基(但し
、芳香族炭化水素基の芳香族環の水素原子はハロゲン原
子、炭素数1〜4のアルキルまたはアルコキシ基で置換
されてもよい)を示し、R^2は炭素数2〜40の2価
の脂肪族炭化水素基、炭素数4〜20の2価の脂環式炭
化水素基、芳香環を形成する炭素数が6〜20である2
価の芳香族炭化水素基(但し芳香族炭化水素基の芳香環
の水素原子はハロゲン原子、炭素数1〜4のアルキル基
またはアルコキシ基で置換されてもよい)、または分子
量80〜8000のポリアルキレンオキシド2価ラジカ
ルを示す〕で表わされる反復単位からなる原料オリゴエ
ステルまたはポリエステルがこれらを構成する反復単位
の量にして5〜95モル%と、一般式(B) HO−R^3COOH………(B) 〔式中R^3は芳香族環を形成する炭素数が6〜20で
ある2価の芳香族炭化水素基(但し芳香族炭化水素基の
水素原子はハロゲン原子、炭素数1〜4のアルキル基ま
たはアルコキシ基で置換されてもよい〕で示されるヒド
ロキシカルボン酸95〜5モル%を反応させて共重合オ
リゴマ−を作り(第1段階)、次にアシル化剤を加えて
アシル化を行ない(第2段階)、さらに減圧下で重合を
行なう(第3段階)3段階からなる反応において、第3
段階の開始前までに、一般式(C) HOR^4OH………(C) (式中R^4は一般式(A)におけるR^1と同義)で
表わされるジヒドロキシ化合物を添加して第3段階開始
前において(A)のOR^2O基100当量に対して 末端OH基当量−末端COOH基当量≧0当量…( I
)(ここで末端OH基、末端COOH基はアシル化され
たものも含む) になるようにして反応させることを特徴とする共重合ポ
リエステルの製造法(1) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(A) [In the formula, R^1 is a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and 4 to 20 carbon atoms. 20 divalent alicyclic hydrocarbon groups or/
and a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms (however, the hydrogen atom of the aromatic ring of the aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms) ), R^2 is a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and 6 to 20 carbon atoms forming an aromatic ring. is 2
valent aromatic hydrocarbon group (however, the hydrogen atom of the aromatic ring of the aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group), or a polyamide with a molecular weight of 80 to 8000. [representing an alkylene oxide divalent radical] The raw material oligoester or polyester consists of a repeating unit represented by the formula (B) HO-R^3COOH... ...(B) [In the formula, R^3 is a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms forming an aromatic ring (however, the hydrogen atom of the aromatic hydrocarbon group is a halogen atom, A copolymerized oligomer is produced by reacting 95 to 5 mol % of a hydroxycarboxylic acid represented by ~4 (optionally substituted with an alkyl group or an alkoxy group) (first step), and then an acylating agent is added to form a copolymerized oligomer. In a reaction consisting of three steps, acylation is carried out (second stage) and polymerization is further carried out under reduced pressure (third stage).
Before the start of the step, a dihydroxy compound represented by the general formula (C) Before starting the third step, terminal OH group equivalent - terminal COOH group equivalent ≧ 0 equivalent for 100 equivalents of OR^2O group in (A)... (I
) (herein, the terminal OH group and the terminal COOH group include those that are acylated).
ようにする特許請求の範囲第1項記載の共重合ポリエス
テルの製造法(2) A method for producing a copolyester according to claim 1, in which the terminal OH group equivalent - the terminal COOH group equivalent ≧ +5 equivalents in formula (I)
フェニレン基である特許請求の範囲第1項記載の製造法(3) In formula (A), 60% or more of R^1 is 1,4-
The manufacturing method according to claim 1, which is a phenylene group.
族炭化水素基である特許請求の範囲第1項記載の製造法(4) The manufacturing method according to claim 1, wherein in formula (A), R^2 is an aliphatic hydrocarbon group having 2 to 6 carbon atoms.
ある特許請求の範囲第1項記載の製造法(5) The manufacturing method according to claim 1, wherein R^1 in formula (A) is a 1,4 phenylene group.
化水素基である特許請求の範囲第1項記載の製造法(6) The manufacturing method according to claim 1, wherein in formula (A), R^2 is an aliphatic hydrocarbon group having 2 carbon atoms.
ある特許請求の範囲第1項記載の製造法(7) The manufacturing method according to claim 1, wherein in formula (B), R^3 is a 1,4 phenylene group
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62013651A JPH07107094B2 (en) | 1987-01-23 | 1987-01-23 | Method for producing copolyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62013651A JPH07107094B2 (en) | 1987-01-23 | 1987-01-23 | Method for producing copolyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63277231A true JPS63277231A (en) | 1988-11-15 |
JPH07107094B2 JPH07107094B2 (en) | 1995-11-15 |
Family
ID=11839124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62013651A Expired - Fee Related JPH07107094B2 (en) | 1987-01-23 | 1987-01-23 | Method for producing copolyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07107094B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009057402A (en) * | 2007-08-29 | 2009-03-19 | Toray Ind Inc | Method for producing liquid crystalline resin |
JP2013517347A (en) * | 2010-01-12 | 2013-05-16 | 三星精密化学株式会社 | Method for producing wholly aromatic liquid crystal polyester resin, wholly aromatic liquid crystal polyester resin produced by the method, and compound of the wholly aromatic liquid crystal polyester resin |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0364533A (en) * | 1989-07-24 | 1991-03-19 | Palitex Project Co Gmbh | Method and apparatus for automatically demounting package adapter from yarn processing machine |
-
1987
- 1987-01-23 JP JP62013651A patent/JPH07107094B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0364533A (en) * | 1989-07-24 | 1991-03-19 | Palitex Project Co Gmbh | Method and apparatus for automatically demounting package adapter from yarn processing machine |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009057402A (en) * | 2007-08-29 | 2009-03-19 | Toray Ind Inc | Method for producing liquid crystalline resin |
JP2013517347A (en) * | 2010-01-12 | 2013-05-16 | 三星精密化学株式会社 | Method for producing wholly aromatic liquid crystal polyester resin, wholly aromatic liquid crystal polyester resin produced by the method, and compound of the wholly aromatic liquid crystal polyester resin |
Also Published As
Publication number | Publication date |
---|---|
JPH07107094B2 (en) | 1995-11-15 |
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