CN109575263B - Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content - Google Patents
Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content Download PDFInfo
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- CN109575263B CN109575263B CN201710904460.0A CN201710904460A CN109575263B CN 109575263 B CN109575263 B CN 109575263B CN 201710904460 A CN201710904460 A CN 201710904460A CN 109575263 B CN109575263 B CN 109575263B
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- adipate
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- butylene succinate
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 40
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 20
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001384 succinic acid Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 150000003609 titanium compounds Chemical class 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- -1 aliphatic organic acid Chemical class 0.000 claims description 18
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 16
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000001361 adipic acid Substances 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 11
- 229920001634 Copolyester Polymers 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 235000010356 sorbitol Nutrition 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 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 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims 1
- 235000011044 succinic acid Nutrition 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000005266 casting Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 238000004448 titration 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
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a preparation method of poly (butylene succinate) -co-adipate-butylene glycol ester with low terminal carboxyl content, which mainly solves the problem that the content of the terminal carboxyl of the poly (butylene succinate) -co-adipate-butylene glycol ester is higher in the prior art. The invention adopts a preparation method of poly (succinic acid) -co-adipic acid-butanediol ester with low-end carboxyl group content, which is characterized in that a polyol composition is added before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes; the technical scheme that the polyol composition is selected from trimethylolpropane and at least one other polyol better solves the problem, and can be used for preparing the poly (butylene succinate) -co-adipate-glycol ester with low carboxyl end group content.
Description
Technical Field
The invention relates to a preparation method of poly (butylene succinate) -co-adipate-butanediol ester with low carboxyl content.
Background
Polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and the like are important synthetic materials, and have a wide range of applications because they have various excellent properties and can be applied to the fields of synthetic fibers, engineering plastics, and the like. However, these polymers cannot be degraded in nature, and the white pollution caused by the polymers is a great problem which besets the world. In order to solve the harm of white pollution to the environment, the development of degradable materials is the trend of future development, and the use ratio of the degradable materials is increased day by day.
Poly succinic acid-co-adipic acid-butanediol ester (PBSA) obtained by copolymerizing succinic acid, adipic acid and 1, 4-butanediol is PBS-based resin with excellent degradation capability, has higher degradation capability than PBS, is easy to process and form, is a mainstream product of degradable film materials, is widely applied to the fields of packaging films, coating films of paper, medical supplies, foam materials, agricultural mulching films and the like, and has huge foreign market demands.
In the preparation of polybutylene succinate-co-adipate-butylene glycol, since butylene glycol is easily decomposed at a high temperature to generate byproducts of tetrahydrofuran and water, a high molecular weight polymer cannot be obtained using a catalyst for preparing an aromatic polyester.
Catalysts used in the prior art for preparing polymers copolymerized from succinic acid, adipic acid and butanediol are titanium alkoxides, tin alkoxides, germanium oxides, etc., as disclosed in patents CN101910245, CN1088945, CN1923872, CN101434689, JP2004018674a2, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin oxide, tin oxide, stannous chloride, germanium compounds, etc.
The titanium catalyst has high activity and no heavy metal, so that the titanium catalyst has no environmental pollution problem, and is particularly suitable for industrial production of aliphatic polyester. In the prior art, the titanate catalyst for preparing the poly (butylene succinate-co-adipate-butylene glycol) has the defects of easy hydrolysis and insoluble precipitation when meeting water, so that the activity of the catalyst is reduced, and the content of terminal carboxyl of a polymer is adversely affected. The high content of terminal carboxyl groups is not favorable for the heat resistance and the processability of the polymer and the stability in the storage process. Chinese patent CN103772683A solves the problem of mutual solubility of titanium compound and butanediol, but does not mention the method of preparing poly (butylene succinate-co-adipate-butylene glycol ester) with low carboxyl group content.
Disclosure of Invention
The invention aims to solve the technical problem of high content of terminal carboxyl of poly (succinic acid) -co-adipic acid-butanediol ester in the prior art, and provides a novel preparation method of poly (succinic acid) -co-adipic acid-butanediol ester with low content of terminal carboxyl. The method has the advantage of effectively reducing the content of the terminal carboxyl of the poly (succinic acid-co-adipic acid-butanediol ester).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content comprises the steps of adding a polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction is finished;
wherein the polyol composition is selected from trimethylolpropane and at least one other polyol.
In the above technical scheme, the polyol composition is trimethylolpropaneThe alkane is combined with at least one other polyol selected from C3～C6One of the polyhydric alcohols, further preferably at least one selected from pentaerythritol, neopentyl glycol, sorbitol, glycerol, xylitol, and mannitol.
In the above technical solution, the weight ratio of trimethylolpropane to other polyols in the polyol composition is preferably 1: (1-15), and more preferably the weight ratio of trimethylolpropane to other polyhydric alcohols is 1: (1-8).
In the above technical solution, the preparation method preferably comprises the following steps: the method comprises the following steps of taking succinic acid, adipic acid and butanediol as raw materials, carrying out esterification reaction by adopting a liquid titanium catalyst under the conditions that the reaction temperature is 150-230 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain an esterification product, and then carrying out polycondensation reaction under the vacuum condition that the reaction temperature is 230-250 ℃ and the reaction pressure is less than 120Pa to obtain the poly (succinic acid) -co-adipic acid-butanediol ester, wherein the used liquid titanium catalyst comprises the reaction product of the following raw materials:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one aliphatic organic acid selected from organic acids;
(D) at least one metal compound selected from IA of the periodic table;
adding the polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes;
wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-20): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-10): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (0-10): 1, the weight ratio of the polyol composition to the copolyester is 0.01-0.4%.
In the above technical solution, it is further preferable that: the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-10): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-5): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (2-6): 1, the weight ratio of the polyol composition to the copolyester is 0.03-0.3%. Based on the weight of the generated poly (butylene succinate) -co-adipate, the addition amount of the catalyst is 50-120 mg/kg in terms of titanium atoms.
In the above-mentioned embodiment, the titanium compound (a) is preferably at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetrabutyl titanate. The diol (B) is preferably at least one selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol. The aliphatic organic acid (C) is preferably at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, and lactic acid. The aliphatic organic acid (C) is an anhydride or a crystalline hydrate. The preferable embodiment of the group IA metal compound (D) is at least one selected from lithium, sodium or potassium.
The preparation method of the liquid titanium catalyst comprises the following steps:
a) reacting a titanium compound with a dihydric alcohol containing 2 to 10 carbon atoms at 20 to 250 ℃ for 0.5 to 25 hours, wherein the titanium compound is Ti (OR)4R is alkyl with 1-10 carbon atoms, white precipitate is separated out, the product is separated after reaction, the residue is washed by distilled water, and the product is dried in vacuum to obtain white powdery substance;
b) adding aliphatic organic acid and IA group metal compound into the white powdery substance obtained in the step a), reacting at the temperature of 30-250 ℃ for 0.5-25 hours to obtain the liquid titanium catalyst for producing the poly (succinic acid) -co-adipic acid-butanediol ester.
According to the invention, the composition formed by combining trimethylolpropane and at least one polyol is added, so that the end-capping probability of terminal hydroxyl is increased, the content of terminal carboxyl of the copolyester is reduced, functional groups which are not contained in a molecular chain of the copolymer are not introduced, and the green environmental protection property of the copolymer is not influenced.
The preparation method of the poly (butylene succinate-co-adipate-glycol ester) with low carboxyl content comprises the following steps:
the known polyester preparation method can be adopted, and succinic acid, adipic acid and butanediol are subjected to esterification reaction at the temperature of 150-230 ℃ and under the reaction pressure of normal pressure-0.5 MPa. And then carrying out polycondensation reaction under the vacuum condition, wherein the reaction temperature is 230-250 ℃, and the reaction pressure is less than 120 Pa. The liquid titanium catalyst is added into the reaction system after the esterification reaction is finished, and the dosage is 50-120 mg/kg (based on the mass of the polycondensation product). The polyol composition of trimethylolpropane in combination with at least one polyol may be added before the start of the esterification reaction, or may be added after the end of the esterification reaction before the start of the polycondensation reaction. And (4) after the polycondensation reaction is finished, casting a belt and granulating to obtain a polymer product.
In the present invention, the intrinsic viscosity and the terminal carboxyl group content of the polybutylene succinate-co-adipate with a low terminal carboxyl group content were measured by the following methods:
a) intrinsic viscosity: the mixture of phenol and tetrachloroethane is used as solvent, and the measurement is carried out at 25 ℃ by using an Ubbelohde viscometer.
b) Content of terminal carboxyl groups: the carboxyl end group content X is calculated according to the following formula and is calculated in units of moles per ton (mol/t).
X＝(V-V0)×c×103/m
In the formula:
v: the volume of the potassium hydroxide-ethanol standard titration solution consumed by the sample solution is a numerical value in milliliters (mL);
V0: the volume of the potassium hydroxide-ethanol standard titration solution consumed by the blank solution is a numerical value in milliliters (mL);
c: the concentration of the potassium hydroxide-ethanol standard titration solution is expressed in mol per liter (mol/L);
m: the sample is weighed in grams (g).
The technical scheme of the invention is that the polyol composition which is formed by adding trimethylolpropane and at least one other polyol and has a general formula of Ti (OR)4Is obtained by the reaction of titanium compound, dihydric alcohol, aliphatic organic acid and IA group metal compoundThe prepared poly (butylene succinate) -co-adipic acid-butylene glycol ester has lower carboxyl end group content which can be less than 10 mol/t; and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Preparation of liquid titanium catalyst A
In a reactor equipped with a stirrer, a condenser and a thermometer, 18.6 g (0.3 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 80 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 27 g (0.3 mol) of lactic acid and 18 g (0.2 mol) of butanediol were added and reacted at 100 ℃ for 3 hours to obtain a pale yellow transparent liquid as catalyst A.
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. Adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 50mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.63dL/g and the content of terminal carboxyl groups to be 29 mol/t.
[ example 1 ]
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. After the esterification, adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 50mg/kg) and a composition of trimethylolpropane and pentaerythritol (the weight ratio of the composition to the copolyester is 0.03%), vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting polycondensation, stopping the reaction after the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling and granulating, and measuring the intrinsic viscosity to be 1.96dL/g and the terminal carboxyl group content to be 12 mol/t.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of liquid titanium catalyst B
In a reactor equipped with a stirrer, a condenser and a thermometer, 18.6 g (0.3 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 100 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 18 g (0.2 mol) of lactic acid, 96 g of a 25% aqueous solution (0.6 mol) of sodium hydroxide and 27 g (0.3 mol) of butanediol were added and reacted at 120 ℃ for 4 hours to obtain a colorless transparent liquid as catalyst B.
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. Adding a catalyst B (based on the mass of the generated polymer, the weight of titanium atoms is 70mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.84dL/g and the content of terminal carboxyl groups to be 30 mol/t.
[ example 2 ]
Preparation of poly (butylene succinate-co-adipate)
280 g of succinic acid, 87 g of adipic acid, 348 g of butanediol, a composition of trimethylolpropane and neopentyl glycol (the weight ratio of the composition to the copolyester is 0.08%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst B (based on the mass of the generated polymer, the weight of titanium atoms is 70mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.98dL/g and the content of terminal carboxyl groups to be 9 mol/t.
[ COMPARATIVE EXAMPLE 3 ]
Preparation of liquid titanium catalyst C
In a reactor equipped with a stirrer, a condenser and a thermometer, 37.2 g (0.6 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 42 g (0.2 mol) of citric acid monohydrate, 48 g of a 25% aqueous sodium hydroxide solution (0.3 mol) and 54 g (0.6 mol) of butanediol were added thereto to react at 90 ℃ for 4 hours to obtain a colorless transparent liquid as catalyst C.
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid and 374 g of butanediol are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst C (based on the mass of the generated polymer, the weight of titanium atoms is 120mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.01dL/g and the content of terminal carboxyl groups to be 35 mol/t.
[ example 3 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 374 g of butanediol, trimethylolpropane and mannitol (the weight ratio of the composition to the copolyester is 0.3%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst C (based on the mass of the generated polymer, the weight of titanium atoms is 120mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.17dL/g and the content of terminal carboxyl groups to be 8 mol/t.
[ COMPARATIVE EXAMPLE 4 ]
Preparation of liquid titanium catalyst D
In a reactor equipped with a stirrer, a condenser and a thermometer, 24.8 g (0.4 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 105 g (0.5 mol) of citric acid monohydrate, 32 g of a 25% aqueous solution (0.2 mol) of sodium hydroxide and 54 g (0.6 mol) of butanediol were added thereto to react at 100 ℃ for 3 hours to obtain a colorless transparent liquid as catalyst D.
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid and 400 g of butanediol are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.86dL/g and the content of terminal carboxyl groups to be 33 mol/t.
[ COMPARATIVE EXAMPLE 5 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 400 g of butanediol and sorbitol (the weight ratio of the sorbitol to the copolyester is 0.25%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.84dL/g and the terminal carboxyl group content to be 31 mol/t.
[ example 4 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 400 g of butanediol, a composition of trimethylolpropane and sorbitol (the weight ratio of the composition to the copolyester is 0.25%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.23dL/g and the content of terminal carboxyl groups to be 10 mol/t.
Claims (7)
1. A preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content is characterized in that a polyol composition is added before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction is finished;
wherein the polyol composition is selected from trimethylolpropane and at least one other polyol;
the other polyhydric alcohol is selected from at least one of pentaerythritol, neopentyl glycol, sorbitol, glycerol, xylitol or mannitol; the weight ratio of trimethylolpropane to other polyols is 1: (1-15).
2. The method of claim 1, wherein the weight ratio of trimethylolpropane to other polyols is 1: (1-8).
3. The preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content according to claim 1 or 2, characterized by comprising the following steps of taking succinic acid, adipic acid and butanediol as raw materials, carrying out esterification reaction by using a liquid titanium catalyst under the conditions that the reaction temperature is 150-230 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain an esterification product, and carrying out polycondensation reaction under the vacuum conditions that the reaction temperature is 230-250 ℃ and the reaction pressure is less than 120Pa to obtain poly (butylene succinate-co-adipate-glycol ester), wherein the used liquid titanium catalyst comprises the reaction product of the following raw materials:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one aliphatic organic acid selected from organic acids;
(D) at least one metal compound selected from IA of the periodic table;
adding the polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes;
wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-20): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-10): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (0-10): 1, the weight ratio of the polyol composition to the copolyester is 0.01-0.4%.
4. The method for preparing poly (butylene succinate-co-adipate) with low carboxyl end group content according to claim 3, wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-10): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-5): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (2-6): 1.
5. the method of claim 3, wherein the weight ratio of the polyol composition to the copolyester is 0.03-0.3%.
6. The method of claim 3, wherein the titanium compound (A) is at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; the dihydric alcohol (B) is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol; the aliphatic organic acid (C) is at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid or lactic acid; the group IA metal compound (D) is at least one selected from lithium, sodium and potassium.
7. The method for preparing low-end carboxyl group content olybuthylenesuccinate-co-adipate-butylene glycol ester according to claim 3, wherein the amount of the catalyst added is 50-120 mg/kg in terms of titanium atom based on the weight of the produced olybuthylenesuccinate-co-adipate-butylene glycol ester.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127421A (en) * | 1979-03-27 | 1980-10-02 | Matsushita Electric Works Ltd | Preparation of polyester resin molding material |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN103408739A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of butyleneadipate-terephthalate with low terminal carboxyl group content |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4396371B2 (en) * | 2004-04-14 | 2010-01-13 | 富士フイルム株式会社 | Magnetic recording medium |
-
2017
- 2017-09-29 CN CN201710904460.0A patent/CN109575263B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127421A (en) * | 1979-03-27 | 1980-10-02 | Matsushita Electric Works Ltd | Preparation of polyester resin molding material |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN103408739A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of butyleneadipate-terephthalate with low terminal carboxyl group content |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
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