CN114672005A - Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate - Google Patents
Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate Download PDFInfo
- Publication number
- CN114672005A CN114672005A CN202210257669.3A CN202210257669A CN114672005A CN 114672005 A CN114672005 A CN 114672005A CN 202210257669 A CN202210257669 A CN 202210257669A CN 114672005 A CN114672005 A CN 114672005A
- Authority
- CN
- China
- Prior art keywords
- reaction
- composite catalyst
- titanate
- titanium
- pbat
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000010936 titanium Substances 0.000 title claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 20
- -1 polybutylene Polymers 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 229920001748 polybutylene Polymers 0.000 title claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000013067 intermediate product Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 48
- 238000005886 esterification reaction Methods 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- 239000001361 adipic acid Substances 0.000 claims description 24
- 235000011037 adipic acid Nutrition 0.000 claims description 24
- 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 17
- 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 9
- 230000032050 esterification Effects 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229920001896 polybutyrate Polymers 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 41
- 238000001816 cooling Methods 0.000 abstract description 14
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 abstract description 11
- 239000004970 Chain extender Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 229920001634 Copolyester Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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 discloses a titanium composite catalyst and a method for synthesizing polybutylene terephthalate-co-adipate (PBAT). The titanium composite catalyst is a white solid prepared by adding titanate, carbonate, phosphoric acid and ethyl orthosilicate into an absolute ethyl alcohol solvent for reaction, reacting for 1-3 hours at 50-90 ℃ to obtain an intermediate product, continuously reacting for 1-2 hours under the condition of slowly dripping deionized water into the intermediate product, cooling the reaction product to room temperature, filtering, and drying in vacuum. The titanium composite catalyst is suitable for preparing PBAT with the molar ratio of aliphatic groups to aromatic groups of 70/30-30/70, a stabilizer and a chain extender are not required to be added, the color phase b value of a PBAT product obtained after direct polycondensation reaction is 4-8, and the melt index MFR (190 ℃,2.16kg) is 3-20 g/10 min.
Description
Technical Field
The invention belongs to the technical field of biodegradable material synthesis, and particularly relates to a titanium composite catalyst and a preparation method thereof for synthesizing polybutylene terephthalate-co-adipate (PBAT).
Background
In recent years, large amounts of waste have created a new source of environmental pollution due to the use of large amounts of plastic products. The development and application of biodegradable polyester materials are one of the main approaches to replace non-degradable plastics and solve the problem of 'white pollution'. The aliphatic-aromatic copolyester has the biodegradability of aliphatic polyester, has the characteristics of high melting point, high crystallization speed, excellent mechanical property and the like of aromatic polyester, and has a very good application prospect. Wherein, the aliphatic-aromatic copolyester synthesized by using Purified Terephthalic Acid (PTA), Adipic Acid (AA) and 1, 4-Butanediol (BDO) as raw materials through esterification reaction and polycondensation reaction is called as polybutylene terephthalate-co-adipate (PBAT).
PBAT has complete biodegradability, excellent processability, and performance equivalent to that of low density polyethylene, and can be processed into express packaging bags, films, mulching films, disposable tableware, etc. The BASF company in foreign countries realizes the industrial production earlier, the companies such as the national tunghe in Xinjiang, Jinfa technology, Jinhuibonglong and the like build industrial production devices in sequence, and along with the issue of the national plastic restriction command in 1 month in 2020, many companies in China continuously promote the construction planning of the PBAT device, and in the future, new PBAT devices with at least millions of production capacity are put into production.
At present, the large-scale PBAT preparation and production all adopt a direct esterification method taking PTA, AA and BDO as raw materials. Catalysts are needed in esterification and polycondensation reaction stages for synthesizing PBAT, and the performance of the catalysts has great influence on the preparation process and the product quality; the good catalyst is required to be convenient to use and difficult to inactivate, and can have good catalytic activity in the esterification and polycondensation reaction processes, the amount of tetrahydrofuran generated by BDO side reaction is small, the side reactions of decarboxylation, cyclization and thermal degradation are also small, the molecular weight of the finally synthesized PBAT product is high, and the PBAT product is expressed as a low melt index MFR test value, a white slice color phase and a low hue b value.
In the synthesis of PBAT, currently, a single-component titanium catalyst is generally applied, for example, titanate catalysts such as tetrabutyl titanate and isopropyl titanate are easily hydrolyzed when meeting water in the reaction process, so that inactivation is caused, and tetrahydrofuran is generated by side reaction; meanwhile, the prepared slices are also low in molecular weight and high in melt index, and usually a chain extender is added for chain extension reaction. There is therefore a need to be able to provide a catalyst system which is highly efficient in the preparation of PBAT, overcoming the disadvantages and shortcomings of the above synthetic processes. The existing catalysts for synthesizing PBAT make many improvements on the preparation method and application, for example: patents CN 101864068, CN 104031246, CN 107216452, CN 112521592, CN 112920391, CN 112794997, etc. Wherein titanate and antimony compound are compounded and then used as a catalyst, some need to be added with methanesulfonic acid as an esterification catalyst, and some need to be added with a stabilizer to improve the hue; most of the catalysts are composite catalysts, some of the catalysts are compounded with rare earth compounds, but the sources of raw materials are limited, the price is high, and the preparation process is complex; some catalysts have complex preparation methods. How to prepare and use a composite catalyst system with high catalytic activity, small side reaction, safety and environmental protection, and how to synthesize a PBAT product with high molecular weight and good hue becomes a research hotspot in the technical field.
Patent CN 101864068 discloses a method for preparing polybutylene terephthalate/adipate butanediol copolyester, wherein the catalyst is antimony catalyst of titanate, antimony acetate, antimony trioxide and ethylene glycol antimony, and phosphorus compound of trimethyl phosphate, triphenyl phosphate and phosphorous acid is added. The method uses the antimony catalyst in a compounding way, antimony belongs to heavy metal, is harmful to the environment and people, does not meet the requirements of safety and environmental protection, and can be eliminated for use.
Patent CN 104031246 discloses a method for preparing all-biobased poly (butylene glycol terephthalate-co-butylene glycol adipate) ester, the adopted catalysts are titanium compound and metal compound, wherein the titanium compound is a compound of titanium dioxide and silicon dioxide, the patent publication does not have detailed technical details and examples to illustrate the compound of titanium dioxide and silicon dioxide, and the effect of actually synthesizing PBAT cannot be supported by data; from similar polyester catalysts, such compounds do not have esterification activity and are also not very active for polymerization.
Patent CN 107216452 discloses a preparation method of a nano titanium rare earth composite catalyst and its application in polyester and copolyester synthesis, wherein the nano rare earth composite catalyst is mainly a liquid phase nano particle suspension prepared from a nano particle dispersion liquid loaded with titanium dioxide and a rare earth compound. The preparation method of the composite catalyst is complex, and chlorides of rare earth elements and the like are introduced in the preparation process; rare earth elements are few in sources, expensive in price and complex in preparation process, when the raw materials are chlorides, the adverse effect of residual chloride ions in the catalyst on the synthesis process is difficult to eliminate, and meanwhile, the rare earth elements are left in the PBAT product and are not friendly to the environment.
Patent CN 112521592 discloses a biodegradable polyester and a preparation method thereof, wherein methanesulfonic acid is added as an esterification catalyst in the esterification-precondensation stage, titanate and other catalysts are added in the polycondensation stage, and a heat stabilizer and an antioxidant are also added in the final polycondensation reaction.
Patent CN 112920391 discloses a preparation method of PBAT for degradable soft products, the catalyst is titanium/silicon organic ester and potassium oxide, carbodiimide is added as stabilizer, and acid anhydride chain extender is also needed.
Patent CN 112794997 discloses a porous composite catalyst, a preparation method thereof and a preparation method of polybutylene terephthalate adipate.
Disclosure of Invention
The technical problem to be solved by the invention is a titanium composite catalyst and a method for synthesizing polybutylene terephthalate-co-adipate, and aims to provide the titanium composite catalyst which is used for preparing a PBAT product, has high reaction activity and small side reaction, and the synthesized PBAT slice has high molecular weight, a minimum melt index MFR (melt flow rate) of 3g/10min, good hue and a hue b value of 4-8.
The invention provides a titanium composite catalyst for preparing copolyester PBAT, which is simple and feasible in preparation method relative to the existing composite catalyst; the catalyst can play a role in catalyzing esterification reaction and polycondensation reaction simultaneously, and can improve the polycondensation reaction rate and the product molecular weight compared with the synthesis of PBAT by taking single titanate as a catalyst; the prepared PBAT product has high molecular weight, does not need to add a chain extender and a stabilizer, has a minimum melt index (190 ℃,2.16kg) of 3g/10min after direct melt polycondensation, has good hue and a b value of 4-8, and overcomes the defects of the PBAT product synthesized by using a single titanate catalyst.
The invention provides a titanium composite catalyst and a preparation method for synthesizing a PBAT product.
The invention aims to prepare the titanium composite catalyst by the following technical scheme, wherein the technical scheme of the titanium composite catalyst comprises the following steps:
titanate, carbonate, phosphoric acid and tetraethoxysilane are added into an absolute ethyl alcohol solvent to react, an intermediate product is obtained after the reaction is carried out for 1-3 hours at the temperature of 50-90 ℃, the reaction is continued for 1-2 hours under the condition that deionized water is slowly dripped into the intermediate product, and the white solid titanium series composite catalyst is prepared after the reaction product is cooled to the room temperature, filtered and dried in vacuum.
In the embodiment of the titanium-based composite catalyst, the titanate is one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and the carbonate is one selected from sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and calcium carbonate.
In the scheme of the titanium composite catalyst, the molar ratio of titanate to carbonate is 1: 1-1: 10, the molar ratio of titanate to phosphoric acid is 10: 1-1: 1, and the molar ratio of titanate to tetraethoxysilane is 10: 1-5: 1.
In the scheme of the titanium composite catalyst, the molar ratio of the use amount of the solvent absolute ethyl alcohol to the titanate is 20: 1-40: 1.
the specific preparation process of the titanium composite catalyst comprises the following steps: adding titanate, carbonate, phosphoric acid and tetraethoxysilane into an absolute ethyl alcohol solvent for reaction, reacting for 1-3 hours at 50-90 ℃ to obtain an intermediate product, continuously reacting for 1-2 hours under the condition of slowly dripping deionized water into the intermediate product, cooling the reaction product to room temperature, filtering, and drying in vacuum to obtain the white solid titanium composite catalyst.
The method for synthesizing the polybutylene terephthalate-co-adipate (PBAT) by utilizing the titanium composite catalyst comprises the steps of adding Pure Terephthalic Acid (PTA), Adipic Acid (AA) and 1, 4-Butanediol (BDO) which are reaction monomers into the titanium composite catalyst, then carrying out esterification reaction to obtain an esterification intermediate product, continuing carrying out polycondensation reaction, and finally preparing the PBAT product.
In the technical scheme for preparing PBAT, the molar ratio of PTA to AA is 30/70-70/30, the sum of the molar ratios of PTA to AA and BDO is 1: (1.1-2.0).
In the above technical scheme for preparing PBAT, the ratio of the amount of the titanium-based composite catalyst added before the reaction to the total mole number of the reaction monomers PTA and AA is 1: (1X 10)3～10×103) The amount of the titanium-based composite catalyst is calculated by the contained titanium element.
In the technical scheme for preparing PBAT, the esterification reaction conditions are that the pressure (gauge pressure) -0.05-0.3 MPa and the temperature is 170-230 ℃; the polycondensation reaction conditions are as follows: the vacuum degree is 50-300 Pa, and the temperature is 220-270 ℃.
In the reaction process, a stabilizer and a chain extender are not required to be added, the final PBAT copolyester product can be obtained through direct polycondensation, the melt index MFR (190 ℃,2.16kg) of the product is 3-20 g/10min along with the difference of the adding amount of the catalyst and the polycondensation reaction time, the color phase of the product is good, the hue b value is 4-8, and the defect that the product synthesized by using a single-component titanium catalyst is yellow is overcome; meanwhile, the synthesized PBAT product has good biodegradability, can be finally degraded into harmless micromolecules in the nature, and can be widely applied to various fields such as express packages, lunch boxes, film bags, foaming materials, disposable products and the like.
The melt index (MFR) of the PBAT chips of the invention was measured according to GB/T3682-2000 at 190 ℃ under a load of 2.16 kg; the b value of PBAT hue is measured by a TC-PIIG full-automatic colorimeter.
The invention has the beneficial effects that:
the titanium composite catalyst does not contain heavy metal antimony and rare earth elements, is a non-toxic or low-toxicity catalyst system, and has no influence on human health and ecological environment.
The titanium composite catalyst prepared by the invention is suitable for preparing PBAT products with the aliphatic/aromatic molar ratio of 30/70-70/30, the catalyst is only required to be added once before the esterification reaction, a stabilizer and the like are not required to be added, the titanium composite catalyst and a chain extender are not required to be added again after the esterification reaction is finished, and the polycondensation reaction can be directly carried out.
The titanium composite catalyst has excellent catalytic activity, the reaction speed is obviously increased, and the polycondensation reaction time is reduced from 6 hours to 3-4 hours compared with a single-component titanium catalyst; the melt index of the product is obviously reduced, and compared with a single-component titanium catalyst, the melt index of the PBAT product is reduced from 30-20 to 20-3.
The catalyst has a stable reaction process, other stabilizers do not need to be added, the synthesized PBAT product has a good hue, and the b value of the hue of the PBAT obtained by catalytic synthesis of the single-component titanium catalyst is 10-15 and is reduced to 4-8.
The preparation method for synthesizing the PBAT does not need to add a chain extender, and can continuously increase the molecular weight of the PBAT product and reduce the melt index under the condition of only prolonging the polycondensation reaction time or not prolonging the polycondensation reaction time and properly increasing the dosage of the catalyst, thereby improving the mechanical and processing properties of the PBAT product.
Detailed Description
Examples 1 to 6 preparation of titanium-based composite catalyst
Example 1
The molar ratio of titanate to carbonate is 1:1, the molar ratio of titanate to phosphoric acid is 10:1, and the molar ratio of titanate to tetraethoxysilane is 5: 1.
Firstly weighing 45.6g (0.2mol) of tetraethyl titanate, 21.2g (0.2mol) of sodium carbonate, 2.0g (0.02mol) of phosphoric acid and 8.3g (0.04mol) of tetraethoxysilane, adding the mixture into 184g (4mol) of absolute ethanol solvent, placing the mixture into a reactor with a reflux device, stirring and reacting for 3 hours at 50 ℃ to obtain an intermediate product, slowly dropwise adding deionized water into the intermediate product to continue reacting for 2 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composite catalyst C1。
Example 2
The molar ratio of titanate to carbonate is 1:10, the molar ratio of titanate to phosphoric acid is 1:1, and the molar ratio of titanate to tetraethoxysilane is 10: 1.
Firstly, 57.0g (0.2mol) of tetraisopropyl titanate, 168g (2mol) of sodium bicarbonate, 19.6g (0.2mol) of phosphoric acid and 4.2g (0.02mol) of ethyl orthosilicate are weighed and added into 368g (8mol) of absolute ethyl alcohol solvent, the mixture is placed into a reactor with a reflux device and stirred for reaction for 1 hour at 90 ℃ to obtain an intermediate product, deionized water is slowly dripped into the intermediate product for continuous reaction for 1 hour, and the white solid titanium composite catalyst C is obtained after the reaction product is cooled to room temperature, filtered and dried in vacuum2。
Example 3
The molar ratio of titanate to carbonate is 1:1, the molar ratio of titanate to phosphoric acid is 5:1, and the molar ratio of titanate to tetraethoxysilane is 10: 1.
Firstly weighing 68g (0.2mol) of tetrabutyl titanate, 27.6g (0.2mol) of potassium carbonate, 3.9g (0.04mol) of phosphoric acid and 4.2g (0.02mol) of ethyl orthosilicate, adding the mixture into 184g (4mol) of absolute ethanol solvent, placing the mixture into a reactor with a reflux device, stirring and reacting the mixture for 3 hours at the temperature of 60 ℃ to obtain an intermediate product, slowly dripping deionized water into the intermediate product to continue reacting for 2 hours, cooling the reaction product to room temperature, filtering and drying the reaction product in vacuum to obtain a white solid titanium composite catalyst C3。
Example 4
The molar ratio of titanate to carbonate is 1:5, the molar ratio of titanate to phosphoric acid is 5:1, and the molar ratio of titanate to tetraethoxysilane is 5: 1.
Firstly, titanic acid IV is weighedAdding 57.0g (0.2mol) of isopropyl ester, 100g (1mol) of potassium bicarbonate, 3.9g (0.04mol) of phosphoric acid and 8.3g (0.04mol) of tetraethoxysilane into 368g (8mol) of absolute ethyl alcohol solvent, placing the mixture in a reactor with a reflux device, stirring and reacting for 1 hour at 90 ℃ to obtain an intermediate product, slowly dropwise adding deionized water into the intermediate product to continue reacting for 1 hour, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composite catalyst C4。
Example 5
The molar ratio of titanate to carbonate is 1:2, the molar ratio of titanate to phosphoric acid is 2:1, and the molar ratio of titanate to tetraethoxysilane is 10: 1.
Firstly weighing 68.0g (0.2mol) of tetrabutyl titanate, 40g (0.4mol) of calcium carbonate, 9.8g (0.1mol) of phosphoric acid and 4.2g (0.02mol) of ethyl orthosilicate, adding the mixture into 230g (5mol) of absolute ethyl alcohol solvent, placing the mixture into a reactor with a reflux device, stirring and reacting for 2 hours at 70 ℃ to obtain an intermediate product, slowly dropwise adding deionized water into the intermediate product to continue reacting for 2 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composite catalyst C5。
Example 6
The molar ratio of titanate to carbonate is 1:6, the molar ratio of titanate to phosphoric acid is 6:1, and the molar ratio of titanate to tetraethoxysilane is 8: 1.
Firstly weighing 45.6g (0.2mol) of tetraethyl titanate, 101g (1.2mol) of sodium bicarbonate, 2.9g (0.03mol) of phosphoric acid and 5.2g (0.025mol) of ethyl orthosilicate, adding into 276g (6mol) of absolute ethanol solvent, placing into a reactor with a reflux device, stirring and reacting for 3 hours at 60 ℃ to obtain an intermediate product, slowly dropwise adding deionized water into the intermediate product to continue reacting for 2 hours, cooling the reaction product to room temperature, filtering, and drying in vacuum to obtain a white solid titanium composite catalyst C6。
Examples 7-13 preparation of PBAT
Example 7
199g (1.2mol) of PTA, 409g (2.8mol) of AA, 396g (4.4mol) of BDO and a titanium composite catalyst C are added into a polymerization reaction kettle1In an amount of 4X 10-3mol, and the dosage condition of the catalyst is as follows: c1/(PTA+AA)＝1:(1×103) Titanium-based composite catalyst C1The total mole number of PTA and AA is (PTA + AA) (the same below) based on the mole number of the titanium-containing element (the same below). Carrying out esterification reaction at 170 ℃ and-0.05 MPa (gauge pressure), and finishing the esterification reaction when the distillate reaches more than 95% of a theoretical value to obtain an intermediate product; gradually reducing the pressure and raising the temperature of a reaction system, carrying out polycondensation reaction at 220 ℃ and under the vacuum degree of 50Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 70/30.
Example 8
465g (2.8mol) PTA, 175g (1.2mol) AA, 720g (8mol) BDO and titanium composite catalyst C are added into a polymerization reaction kettle2In an amount of 4X 10-4mol, and the dosage condition of the catalyst is as follows: c2/(PTA+AA)＝1:(10×103). Carrying out esterification reaction at 230 ℃ and 0.3MPa (gauge pressure), and finishing the esterification reaction when the distillate reaches more than 95% of a theoretical value to obtain an intermediate product; gradually reducing the pressure and raising the temperature of a reaction system, carrying out polycondensation reaction at 270 ℃ and the vacuum degree of 300Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, granulating, and synthesizing to obtain a PBAT product with the aliphatic/aromatic ratio of 30/70.
Example 9
266g (1.6mol) of PTA, 350g (2.4mol) of AA, 540g (6mol) of BDO and a titanium composite catalyst C are added into a polymerization reaction kettle3In an amount of 8X 10-4mol, and the dosage condition of the catalyst is as follows: c3/(PTA+AA)＝1:(5×103). Carrying out esterification reaction at 230 ℃ and-0.05 MPa (gauge pressure), and finishing the esterification reaction when the distillate reaches more than 95% of a theoretical value to obtain an intermediate product; and gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 50Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 60/40.
Example 10
332g (2mol) of PTA and 292g (2mol) of A were charged into a polymerization reactorA. 540g (6mol) of BDO and titanium composite catalyst C4In an amount of 8X 10-4mol, and the catalyst dosage condition is as follows: c4/(PTA+AA)＝1:(5×103). Carrying out esterification reaction at 200 ℃ and-0.05 MPa (gauge pressure), and when the distillate reaches more than 95% of the theoretical value, finishing the esterification reaction to obtain an intermediate product; and gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at the temperature of 240 ℃ and the vacuum degree of 100Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 50/50.
Example 11
332g (2mol) of PTA, 292g (2mol) of AA, 540g (6mol) of BDO and a titanium composite catalyst C are added into a polymerization reaction kettle5In an amount of 8X 10-4mol, and the dosage condition of the catalyst is as follows: c5/(PTA+AA)＝1:(5×103). Carrying out esterification reaction at 170 ℃ and-0.05 MPa (gauge pressure), and finishing the esterification reaction when the distillate reaches more than 95% of a theoretical value to obtain an intermediate product; and gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 100Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 50/50.
Example 12
266g (1.6mol) of PTA, 350g (2.4mol) of AA, 540g (6mol) of BDO and a titanium composite catalyst C are added into a polymerization reaction kettle6In an amount of 4X 10-4mol, and the dosage condition of the catalyst is as follows: c6/(PTA+AA)＝1:(10×103). The esterification reaction is carried out at 230 ℃ and 0.3MPa (gauge pressure), and when the distillate reaches more than 95% of the theoretical value, the esterification reaction is finished to obtain an intermediate product. And gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 50Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 60/40.
Example 13
332g (2) was charged into a polymerization reactorThe amounts of the PTA (mol), the AA (292 g (2 mol)), the BDO (540 g (6 mol)) and the titanium composite catalyst are 8 multiplied by 10-4mol, and the dosage condition of the catalyst is as follows: c1/(PTA+AA)＝1:(5×103). Carrying out esterification reaction at 210 ℃ and-0.05 MPa (gauge pressure), and finishing the esterification reaction when the distillate reaches more than 95% of the theoretical value to obtain an intermediate product; and gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at the temperature of 240 ℃ and the vacuum degree of 100Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBAT product with the aliphatic/aromatic ratio of 50/50.
The experimental results of the preparation of the titanium composite catalysts used in examples 7 to 13 are shown in table 1, and the number of moles of the titanium composite catalyst is based on the titanium element contained.
Comparative example 1
PBAT with an aliphatic/aromatic ratio of 50/50 was prepared in the same manner as in example 10, except that tetrabutyl titanate (TBT), a one-component titanium-based catalyst, was added before esterification in an amount of 4X 10-4mol, adding TBT 6X 10 in the intermediate product again after the esterification reaction is finished-4After mol, the polycondensation reaction is carried out, and the mole number of the TBT is calculated by the contained titanium element, and the result is shown in Table 1.
Comparative example 2
PBAT having an aliphatic/aromatic ratio of 50/50 was prepared in the same manner as in example 13, except that tetraisopropyl titanate (TPT), a one-component titanium-based catalyst, was added in an amount of 5X 10 before esterification-4mol, adding TPT into the intermediate product again after the esterification reaction is finished, wherein the TPT is 3.5 multiplied by 10-3After mol, the polycondensation reaction was carried out, and the results are shown in Table 1, wherein TPT is used in mol based on the contained titanium element.
TABLE 1 results of experimental preparation of PBAT
As can be seen from Table 1, examples 7 to 13 are compared with comparative examples 1 and 2; when the melt index is close to the melt index, the polycondensation time of the titanium composite catalyst is reduced compared with that of the single titanate catalyst; when the titanium composite catalyst is used, the melt index MFR (190 ℃, 2.16kg) of the PBAT product obtained by direct polycondensation can be as low as 3; and the hue b value is better, and is reduced to 4-8 from 10-15 in the single titanate catalytic reaction.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications of the methods and techniques described herein may be practiced without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (8)
1. A titanium composite catalyst is characterized in that titanate, carbonate, phosphoric acid and ethyl orthosilicate are added into an absolute ethyl alcohol solvent to react, an intermediate product is obtained after the reaction is carried out for 1-3 hours at the temperature of 50-90 ℃, the reaction is continued for 1-2 hours under the condition that deionized water is dripped into the intermediate product, and the white solid titanium composite catalyst is prepared after the reaction product is cooled to room temperature, filtered and dried in vacuum.
2. The titanium-based composite catalyst according to claim 1, wherein the titanate is one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; the carbonate is selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or calcium carbonate.
3. The titanium-based composite catalyst according to claim 1, wherein the molar ratio of titanate to carbonate is 1:1 to 1:10, the molar ratio of titanate to phosphoric acid is 10:1 to 1:1, and the molar ratio of titanate to ethyl orthosilicate is 10:1 to 5: 1.
4. The titanium-based composite catalyst according to claim 1, wherein the molar ratio of the amount of the solvent absolute ethyl alcohol to the titanate is 20: 1-40: 1.
5. the method for synthesizing polybutylene terephthalate-co-adipate by applying the titanium composite catalyst of claim 1 is characterized in that reaction monomers of pure terephthalic acid PTA, adipic acid AA and 1, 4-butanediol BDO are subjected to esterification reaction after being added with the titanium composite catalyst to obtain an esterification intermediate product, and then the polycondensation reaction is continued to prepare PBAT finally; wherein:
the molar ratio of the PTA to the AA in the reaction monomer is 30/70-70/30, the ratio of the sum of the molar numbers of the PTA and the AA to the molar number of the BDO is 1: (1.1-2.0).
6. The method according to claim 5, wherein the esterification reaction is carried out under conditions of a pressure gauge of-0.05 to 0.3MPa and a temperature of 170 to 230 ℃; the polycondensation reaction conditions are as follows: the vacuum degree is 50-300 Pa, and the temperature is 220-270 ℃.
7. The method of claim 5, wherein the ratio of the amount of the titanium-based composite catalyst added before the reaction to the total molar number of the reaction monomers PTA and AA is 1: (1X 10)3～10×103) The amount of the titanium-based composite catalyst is based on the titanium element contained.
8. The method of claim 5, wherein the melt index MFR (190 ℃,2.16kg) of PBAT prepared by the direct polycondensation is 3 to 20g/10min, and the hue b value of PBAT chips is 4 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210257669.3A CN114672005B (en) | 2022-03-16 | Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210257669.3A CN114672005B (en) | 2022-03-16 | Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672005A true CN114672005A (en) | 2022-06-28 |
| CN114672005B CN114672005B (en) | 2024-06-11 |
Family
ID=
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278971A (en) * | 2000-03-30 | 2001-10-10 | Teijin Ltd | Polyester production method |
| CN1450098A (en) * | 2003-04-18 | 2003-10-22 | 上海华明高技术（集团）有限公司 | Process for preparing polyester and copolyester |
| JP2006265536A (en) * | 2005-02-25 | 2006-10-05 | Mitsubishi Chemicals Corp | Process for continuous production of polyester, polyester prepolyer granule and polyester |
| CN101173038A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing polyester |
| 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 |
| CN101864068A (en) * | 2009-04-15 | 2010-10-20 | 中国石油天然气股份有限公司 | Preparation method of polybutylene terephthalate/adipate butanediol copolyester |
| US20110162205A1 (en) * | 2008-09-08 | 2011-07-07 | Shanghai Huaming Hi-Tech (Group) Co., Ltd | Catalyst for producing polybutylene succinate or copolyester thereof, and preparing mehtods of the catalyst |
| CN102382287A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Liquid titanium catalyst for polyester and copolyester and preparation method thereof |
| CN102702497A (en) * | 2012-06-07 | 2012-10-03 | 昆山天洋热熔胶有限公司 | Preparation method of polyester catalyst |
| CN102924698A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
| US20160376403A1 (en) * | 2015-04-13 | 2016-12-29 | Nanjing University | Method for synthesizing poly(butylene adipate-co-terephthalate) |
| WO2018058735A1 (en) * | 2016-09-30 | 2018-04-05 | 北京市化学工业研究院 | Method for synthesizing resin for degradable membrane material with high molecular weight and high barrier property |
| CN108034046A (en) * | 2017-11-23 | 2018-05-15 | 中国科学院理化技术研究所 | A kind of high efficiency polyester composite catalyst and its preparation method and application |
| CN113388100A (en) * | 2021-05-28 | 2021-09-14 | 中国石油化工股份有限公司 | Catalyst system for synthesis of aliphatic-aromatic copolyester and application thereof |
| CN113881027A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Titanium polyester catalyst and preparation method and application thereof |
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278971A (en) * | 2000-03-30 | 2001-10-10 | Teijin Ltd | Polyester production method |
| CN1450098A (en) * | 2003-04-18 | 2003-10-22 | 上海华明高技术（集团）有限公司 | Process for preparing polyester and copolyester |
| JP2006265536A (en) * | 2005-02-25 | 2006-10-05 | Mitsubishi Chemicals Corp | Process for continuous production of polyester, polyester prepolyer granule and polyester |
| CN101173038A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing polyester |
| US20110162205A1 (en) * | 2008-09-08 | 2011-07-07 | Shanghai Huaming Hi-Tech (Group) Co., Ltd | Catalyst for producing polybutylene succinate or copolyester thereof, and preparing mehtods of the catalyst |
| CN101864068A (en) * | 2009-04-15 | 2010-10-20 | 中国石油天然气股份有限公司 | Preparation method of polybutylene terephthalate/adipate butanediol copolyester |
| 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 |
| CN102382287A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Liquid titanium catalyst for polyester and copolyester and preparation method thereof |
| CN102702497A (en) * | 2012-06-07 | 2012-10-03 | 昆山天洋热熔胶有限公司 | Preparation method of polyester catalyst |
| CN102924698A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
| US20160376403A1 (en) * | 2015-04-13 | 2016-12-29 | Nanjing University | Method for synthesizing poly(butylene adipate-co-terephthalate) |
| WO2018058735A1 (en) * | 2016-09-30 | 2018-04-05 | 北京市化学工业研究院 | Method for synthesizing resin for degradable membrane material with high molecular weight and high barrier property |
| CN108034046A (en) * | 2017-11-23 | 2018-05-15 | 中国科学院理化技术研究所 | A kind of high efficiency polyester composite catalyst and its preparation method and application |
| CN113881027A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Titanium polyester catalyst and preparation method and application thereof |
| CN113388100A (en) * | 2021-05-28 | 2021-09-14 | 中国石油化工股份有限公司 | Catalyst system for synthesis of aliphatic-aromatic copolyester and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| NIU, XS ET AL.: "Preparation and structure analysis of α-Fe2O3 nanocrystalline in 2-methoxyethanol system", 《JOURNAL OF INORGANIC MATERIALS》, vol. 16, no. 2, 1 March 2001 (2001-03-01), pages 243 - 248 * |
| 张大省;: "钛系催化剂在聚对苯二甲酸乙二醇酯合成中的应用", 纺织导报, no. 01, 8 January 2020 (2020-01-08), pages 48 - 52 * |
| 王晓慧;付志峰;石艳;史君;陈颖;: "直接酯化法合成聚(对苯二甲酸丁二醇-co-己二酸丁二醇)可生物降解共聚酯", 石油化工, vol. 39, no. 11, 15 November 2010 (2010-11-15), pages 1273 - 1278 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3897756B2 (en) | Catalyst for producing polyester and method for producing polyester using the same | |
| EP2184309B1 (en) | Process for producing a polycondensation catalyst for producing polyester | |
| CN112266471B (en) | Preparation method of polybutylene adipate-terephthalate | |
| KR101270863B1 (en) | Catalyst for polyester polycondensation and method for producing polyester resin using the same | |
| TW201127871A (en) | Process for making polyethylene terephthalate | |
| EP2479204A1 (en) | Polycondensation catalyst for the production of polyesters, and polyester production method using same | |
| WO2016011939A1 (en) | Process method for synthesizing poly(butylene succinate-co-butylene adipate) catalyzed by biomass creatinine | |
| CN101104678A (en) | Method for preparing titanium catalyst polyester | |
| WO2023202449A1 (en) | Solid bimetallic titanium-based polyester catalyst, preparation method therefor, and use thereof | |
| US3714125A (en) | Aromatic ortho-carbamates added to polyester polycondensation | |
| CN114891189B (en) | Preparation method of low-chroma PETG copolyester | |
| CN111607074B (en) | Method for preparing terephthalic acid-ethylene glycol-isosorbide copolyester by antimony-titanium bimetallic catalysis | |
| KR101496634B1 (en) | Method for preparing polyester resin copolymerized with neopentyl glycol | |
| EP2881416A1 (en) | Polycondensation catalyst for polyester production and production of polyester using polycondensation catalyst for polyester production | |
| CN114672005A (en) | Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate | |
| CN114672005B (en) | Titanium composite catalyst and method for synthesizing polybutylene terephthalate-co-adipate | |
| KR101386223B1 (en) | Catalyst composition for preparing polyesters, and method for preparing polyesters using the same | |
| CN113388100B (en) | Catalyst system for synthesizing aliphatic-aromatic copolyester and application thereof | |
| CN116874755A (en) | Composite titanium catalyst and preparation method and application thereof | |
| CN115873223A (en) | Preparation method of poly terephthalic acid-butylene carbonate | |
| CN116284712A (en) | Environment-friendly polyester film and preparation method thereof | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| CN114075330B (en) | Aluminum polyester catalyst and preparation method and application thereof | |
| EP3048125A1 (en) | Polyester production method | |
| CN114621425B (en) | Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |