CN114057996A - Efficient synthesis method of terephthalic acid-based polyester - Google Patents
Efficient synthesis method of terephthalic acid-based polyester Download PDFInfo
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- CN114057996A CN114057996A CN202111525415.7A CN202111525415A CN114057996A CN 114057996 A CN114057996 A CN 114057996A CN 202111525415 A CN202111525415 A CN 202111525415A CN 114057996 A CN114057996 A CN 114057996A
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- reaction
- polycondensation
- esterification
- terephthalic acid
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920000728 polyester Polymers 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000005886 esterification reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- AZLGDNBTDKZORI-UHFFFAOYSA-N tris(3-methylphenyl) phosphite Chemical compound CC1=CC=CC(OP(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 AZLGDNBTDKZORI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
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- 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 provides a high-efficiency synthesis method of terephthalic acid-based polyester, which takes terephthalic acid and a plurality of dihydric alcohols as raw materials and obtains high-quality polyester through esterification, pre-polycondensation and post-polycondensation processes in sequence. Wherein the catalyst is a composite catalyst consisting of an esterification catalyst, a polymerization catalyst and a stabilizer and is added in sections; the postcondensation adopts a continuous production process, avoids material back mixing, effectively reduces the occurrence of side reactions, improves the reaction efficiency and the reaction stability, and obviously improves the indexes of the product such as viscosity, carboxyl end group content, chroma and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing terephthalic acid-based polyester.
Background
Polyester is a general name of polymers obtained by condensation polymerization of dibasic acid and dihydric alcohol, and is a plastic material with excellent performance and wide application. For example, polyethylene terephthalate (PET) produced by polycondensation of terephthalic acid and ethylene glycol can be used as a fiber for clothing weaving, and can also be used as a bottle material for a packaging material. Polybutylene terephthalate (PBT) produced by polycondensation of terephthalic acid and 1, 4-butanediol is one of five engineering plastics, and is widely applied to the fields of automobiles, electronics and electricity and the like due to good heat resistance, weather resistance and fatigue resistance of the PBT. In recent years, research focuses on degradable plastics, which are mainly made of polyester materials, including polybutylene terephthalate-adipate-butylene glycol (PBAT), polybutylene succinate (PBS), polypropylene carbonate (PPC), and the like.
Among the above polymers, the polyester having terephthalic acid as a raw material and a building unit occupies an absolute ratio, not only because the terephthalic acid raw material is easily available and low in cost, but also because the downstream materials have excellent application properties.
The synthesis process of the polyester mainly comprises an ester exchange method and a direct esterification method. The ester exchange method is that dimethyl terephthalate is used as raw material, and through ester exchange reaction with dihydric alcohol, intermediate product is formed, and then polyester is produced through polycondensation under certain conditions, and methanol and excessive dihydric alcohol are removed in the reaction process. The direct esterification method is that terephthalic acid and dihydric alcohol directly undergo esterification reaction, water molecules are removed, and then polyester is generated by polycondensation under certain conditions. The transesterification process requires less energy than the two processes, but the production costs are high due to the recycling of methanol. Therefore, the direct esterification method is gradually becoming the mainstream process of polyester synthesis.
Due to the higher boiling point of the glycols, high temperatures and high vacuum levels are often required during the removal process, and longer reaction times are required. Under high temperature, long time reaction conditions, thermal degradation reactions of the polyester can result, resulting in reduced product viscosity, loss of clarity, and high color formation. Therefore, the method improves the polycondensation reaction rate and accelerates the removal of the dihydric alcohol, and becomes the key of polyester synthesis.
Currently, the industrial synthesis of polyesters is mainly based on tank reactions. The traditional kettle type polycondensation reaction has the problem of back mixing, and is not favorable for removing micromolecular byproducts from reactants in time. Therefore, the improvement of the kettle reaction process becomes the main direction of the research of polyester synthesis.
Disclosure of Invention
In view of the above, the present invention provides a method for efficiently synthesizing terephthalic acid-based polyester, so as to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high-efficiency synthesis method of terephthalic acid-based polyester comprises the following steps:
1) each apparatus was purged with nitrogen before the reaction.
2) Adding terephthalic acid and dihydric alcohol into an esterification reaction kettle according to a certain proportion, simultaneously adding a composite catalyst to start reaction, and ending the esterification reaction when the water yield reaches 90% of the theoretical amount.
3) And (3) feeding the esterification reaction liquid into a pre-polycondensation reaction kettle, controlling the reaction pressure by a vacuum pump, and ending the pre-polycondensation when the liquid output reaches 90% of the mass of the excessive dihydric alcohol.
4) And (3) feeding the pre-polycondensation reaction liquid into a post-polycondensation reactor, controlling the reaction pressure through a vacuum pump, and controlling the time for discharging.
Or:
1) each apparatus was purged with nitrogen before the reaction.
2) Adding terephthalic acid and dihydric alcohol into an esterification reaction kettle according to a certain proportion, and simultaneously adding an esterification catalyst;
3) heating the esterification reaction kettle for reaction, timing from the distillation of the liquid, and ending the esterification reaction when the water yield reaches 90% of the theoretical amount;
4) transferring the reaction material from the esterification reaction kettle to a pre-polycondensation reaction kettle through a gear pump, simultaneously adding a polymerization catalyst, controlling the reaction pressure through a vacuum pump, timing from the distillation of liquid, and ending the pre-polycondensation when the liquid output reaches 90% of the mass of the excessive dihydric alcohol;
5) transferring the reaction material from the pre-polycondensation reaction kettle to a post-polycondensation reactor through a gear pump, simultaneously adding a stabilizer, controlling the reaction pressure through a vacuum pump, and controlling the post-polycondensation reaction time through the gear pump flow;
6) after the post-polycondensation reaction is finished, transferring the product into water for rapid cooling and pelletizing.
The C2-C12 dihydric alcohol is one or more than two of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 10-decanediol and dodecanediol, and the molar ratio of the addition amount to the terephthalic acid is 1.05-1.60.
The composite catalyst comprises three components of an esterification catalyst, a polymerization catalyst and a stabilizer; wherein the esterification catalyst is one or more of zinc acetate, cobalt acetate, aluminum acetate and magnesium acetate; the polymerization catalyst is one or more of antimony trioxide, ethylene glycol antimony, germanium oxide, titanium dioxide, isopropyl titanate and butyl titanate; the stabilizer is one or more than two of trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, triphenyl phosphite and tri-m-toluyl phosphite. The dosage of the composite catalyst is equivalent to 100-1000 ppm of the mass of the terephthalic acid.
The esterification reaction is carried out in a reaction kettle, the temperature is 200-240 ℃, the pressure is controlled to be 0-0.5 MPaG, the stirring speed is 50-200 rpm, and the reaction time is 1-4 h.
The pre-polycondensation reaction is carried out in a reaction kettle, the temperature is 220-260 ℃, the pressure is controlled to be 5-50 kPaA, the stirring speed is 50-200 rpm, and the reaction time is 0.5-2 h.
The post-polycondensation reaction is carried out in equipment such as a horizontal polycondensation kettle, a falling film evaporator, a packed tower and the like, the temperature is 220-300 ℃, the pressure is controlled at 50 Pa-1 kPa, and the reaction time is 0.1-1 h.
Compared with the prior art, the efficient synthesis method of the terephthalic acid-based polyester has the following advantages:
(1) the mode of adding the composite catalyst step by step is adopted, so that the side reaction of the polymerization catalyst in the esterification stage is avoided, and the oxidation side reaction in the later stage of polycondensation is reduced;
(2) the polycondensation reaction adopts a two-stage vacuum reactor, wherein the post-polycondensation reactor can realize continuous discharge, thereby avoiding material back-mixing, being beneficial to removing micromolecular byproducts, and effectively reducing the occurrence of thermal decomposition side reaction while reducing the polycondensation time;
(3) the obtained polymer product has obviously improved indexes such as viscosity, carboxyl end group content, chroma and the like.
In conclusion, the method improves reaction efficiency, reaction stability and product quality.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a process flow of a terephthalic acid-based polyester according to examples 1 to 4 of the present invention;
FIG. 2 is a schematic view of the process flow of synthesizing terephthalic acid-based polyester by the conventional ester exchange method and the direct esterification method.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs.
The invention will be described in detail with reference to the following examples.
Example 1: preparation of polyethylene terephthalate (PET)
Putting 1800g of terephthalic acid and 706g (excessive 5 mol%) of ethylene glycol into an esterification reaction kettle, adding 0.3g of zinc acetate, replacing with nitrogen, heating to 200 ℃, starting timing, controlling the pressure to be 0.20-0.30 MpaA, and stirring at the speed of 50 rpm. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, simultaneously adding 0.3g of ethylene glycol antimony, controlling the temperature at 230 ℃, the pressure at 5-8 kPaA and the stirring speed at 150rpm, and reacting for 1 hour to obtain 30.0g of liquid outlet. And transferring the reaction liquid to a post-polycondensation horizontal reaction kettle through a gear pump, simultaneously adding 0.1g of triethyl phosphite, controlling the temperature at 260 ℃, the pressure at 100-300 Pa, and averagely keeping the residence time at 0.5 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PET polyester by infrared and nuclear magnetic detection.
Example 2: preparation of polybutylene terephthalate (PBT)
Putting 1800g of terephthalic acid and 1073g (excessive 10 mol%) of 1, 4-butanediol into an esterification reaction kettle, adding 0.4g of aluminum acetate, replacing with nitrogen, heating to 230 ℃, starting timing, controlling the pressure to be 0.20-0.30 MPaA, and stirring at the speed of 200 rpm. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, simultaneously adding 0.4g of butyl titanate, controlling the temperature to be 240 ℃, the pressure to be 5-10 kPaA, stirring at the speed of 200rpm, and reacting for 1 hour to obtain 88.0g of liquid outlet. And transferring the reaction liquid to a post-polycondensation packed tower through a gear pump, adding 0.2g of trimethyl phosphite at the same time, controlling the temperature at 260 ℃, the pressure at 80-200 Pa, and averagely keeping the residence time at 0.5 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PBT polyester by infrared and nuclear magnetic detection.
Example 3: preparation of polyethylene terephthalate glycol-1, 4-cyclohexanedimethanol copolyester (PETG)
Putting 1800g of terephthalic acid, 538g of ethylene glycol and 468g of 1, 4-cyclohexanedimethanol (the total amount of binary components is excessive by 10 mol%) into an esterification reaction kettle, adding 0.3g of magnesium acetate, replacing with nitrogen, heating to 200 ℃, starting timing, controlling the pressure to be 0.20-0.30 MPaA, and stirring at the speed of 100 rpm. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, simultaneously adding 0.3g of ethylene glycol antimony, controlling the temperature at 230 ℃, the pressure at 5-7 kPaA and the stirring speed at 150rpm, and reacting for 1h to obtain 154.0g of liquid outlet. And transferring the reaction liquid to a post-polycondensation horizontal reaction kettle through a gear pump, simultaneously adding 0.1g of tri-m-toluyl phosphite, controlling the temperature at 270 ℃, the pressure at 100-200 Pa, and averagely keeping the residence time at 0.6 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PETG copolyester by infrared and nuclear magnetic detection.
Example 4: preparation of 1, 4-Cyclohexanedimethanol Polyterephthalate (PCT)
Putting 1800g of terephthalic acid and 1796g (excessive 15 mol%) of 1, 4-butanediol into an esterification reaction kettle, adding 0.3g of cobalt acetate, replacing with nitrogen, heating to 240 ℃, starting timing, controlling the pressure to be 0-0.05 MPaA, and stirring at the speed of 150 rpm. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, simultaneously adding 0.3g of butyl titanate, controlling the temperature at 260 ℃, the pressure at 5-10 kPaA, stirring at the speed of 100rpm, and reacting for 1 hour to obtain 211.0g of liquid outlet. And transferring the reaction liquid to a post-polycondensation falling-film evaporator through a gear pump, simultaneously adding 0.1g of triphenyl phosphite, controlling the temperature at 295 ℃, the pressure at 60-100 Pa, and averagely keeping the residence time at 0.6 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PCT polyester by infrared and nuclear magnetic detection, and the intrinsic viscosity [ eta ] of the product is 0.702dL/g according to GB/T14190-2008.
Example 5: preparation of polybutylene terephthalate (PBT)
Putting 1800g of terephthalic acid and 1073g (excessive 10 mol%) of 1, 4-butanediol into an esterification reaction kettle, adding a composite catalyst consisting of 0.4g of magnesium acetate, 0.4g of isopropyl titanate and 0.2g of triphenyl phosphite, replacing nitrogen, heating to 220 ℃, starting timing, controlling the pressure to be 0.25-0.35 MPaA, and stirring at the speed of 50 rpm. After 2h reaction, the liquid yield was 180 g. And (3) transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, controlling the temperature at 245 ℃, the pressure at 5-15 kPaA, stirring at the speed of 50rpm, and reacting for 1 hour to obtain 90.0g of liquid. And transferring the reaction liquid to a post-polycondensation packed tower through a gear pump, controlling the temperature to be 250 ℃, the pressure to be 80-200 Pa, and averagely keeping the residence time to be 0.5 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PBT polyester by infrared and nuclear magnetic detection.
Example 6: preparation of polyethylene terephthalate (PET)
Putting 1800g of terephthalic acid and 682g (excessive 4 mol%) of ethylene glycol into an esterification reaction kettle, adding a composite catalyst consisting of 0.3g of cobalt acetate, 0.4g of germanium oxide and 0.2g of trimethyl phosphite, replacing nitrogen, heating to 225 ℃, starting timing, controlling the pressure to be 0.25-0.3 MPaA, and stirring at the speed of 100 rpm. After 3h reaction, the effluent amount was 170 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, controlling the temperature to be 235 ℃, the pressure to be 5-20 kPaA, stirring at the speed of 100rpm, and reacting for 1.5h to obtain 50.0g of liquid outlet. And transferring the reaction liquid to a post-condensation packed tower through a gear pump, controlling the temperature to be 270 ℃, the pressure to be 100-300 Pa, and averagely keeping the residence time to be 1 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PET polyester by infrared and nuclear magnetic detection.
Comparative example 1: preparation of 1, 4-Cyclohexanedimethanol Polyterephthalate (PCT)
Compared with the example 4, the post-polycondensation reactor is changed into a reaction kettle. Putting 1800g of terephthalic acid and 1796g (excessive 15 mol%) of 1, 4-butanediol into an esterification reaction kettle, adding 0.3g of cobalt acetate, replacing with nitrogen, heating to 240 ℃, starting timing, and controlling the pressure to be 0-0.05 MPaA. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, adding 0.3g of butyl titanate, controlling the temperature at 260 ℃ and the pressure at 5-10 kPaA, and reacting for 1 hour to obtain 211.0g of liquid outlet. And transferring the reaction liquid to a post-polycondensation reaction kettle through a gear pump, simultaneously adding 0.1g of triphenyl phosphite, controlling the temperature at 295 ℃ and the pressure at 60-100 Pa, reacting for 1.0h, and discharging. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PCT polyester by infrared and nuclear magnetic detection, and the intrinsic viscosity [ eta ] of the product is 0.623dL/g according to GB/T14190-2008.
Comparative example 2: preparation of 1, 4-Cyclohexanedimethanol Polyterephthalate (PCT)
In contrast to example 4, no stabilizer was added in the finishing stage. Putting 1800g of terephthalic acid and 1796g (excessive 15 mol%) of 1, 4-butanediol into an esterification reaction kettle, adding 0.3g of cobalt acetate, replacing with nitrogen, heating to 240 ℃, starting timing, and controlling the pressure to be 0-0.05 MPaA. After 2h reaction, the effluent amount was 176 g. And transferring the reaction liquid to a pre-polycondensation reaction kettle through a gear pump, adding 0.3g of butyl titanate, controlling the temperature at 260 ℃ and the pressure at 5-10 kPaA, and reacting for 1 hour to obtain 211.0g of liquid outlet. And transferring the reaction liquid to a post-condensation falling-film evaporator through a gear pump, controlling the temperature at 295 ℃, the pressure at 60-100 Pa, and averagely keeping the residence time for 0.6 h. And discharging the final reaction product through a gear pump, and transferring the product into water for rapid cooling and granulation.
The product is proved to be PCT polyester by infrared and nuclear magnetic detection, and the intrinsic viscosity [ eta ] of the product is 0.678dL/g determined according to GB/T14190-2008.
The product results of the above examples and comparative examples are summarized in table 1.
TABLE 1 summary of product results for examples and comparative examples
Comparing example 4 with comparative example 1, it can be seen that: the adoption of the continuous discharging mode can not only reduce the reaction time, but also improve the intrinsic viscosity of the polyester.
Comparing example 4 with comparative example 2, it can be seen that: by adding the stabilizer, the side oxidation reaction can be effectively reduced, and the intrinsic viscosity and the product quality of the polyester can be improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. A high-efficiency synthesis method of terephthalic acid-based polyester is characterized by comprising the following steps:
firstly, mixing terephthalic acid with dihydric alcohol of C2-C12;
and secondly, adding a composite catalyst into the mixture obtained in the first step, and carrying out esterification reaction, pre-polycondensation reaction and post-polycondensation reaction to obtain the high-quality polyester.
2. The method of claim 1, wherein: the molar ratio of the addition amount of the C2-C12 dihydric alcohol to the terephthalic acid is 1.05-1.60, and the dosage of the composite catalyst is 100-1000 ppm of the mass of the terephthalic acid.
3. The method of claim 2, wherein: the composite catalyst comprises three components of an esterification catalyst, a polymerization catalyst and a stabilizer; the mixing modes of the C2-C12 dihydric alcohol, the terephthalic acid and the composite catalyst are two:
directly mixing C2-C12 dihydric alcohol, terephthalic acid and a composite catalyst;
or mixing the C2-C12 dihydric alcohol and the terephthalic acid with an esterification catalyst, mixing the esterification reaction liquid with a polymerization catalyst after the esterification reaction is finished, and mixing the pre-polycondensation reaction liquid with a stabilizer after the pre-polycondensation reaction is finished.
4. The method of claim 3, wherein: the added C2-C12 dihydric alcohol is one or more than two of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 10-decanediol and dodecanediol; the esterification catalyst is one or more than two of zinc acetate, cobalt acetate, aluminum acetate and magnesium acetate; the polymerization catalyst is one or more of antimony trioxide, ethylene glycol antimony, germanium oxide, titanium dioxide, isopropyl titanate and butyl titanate; the stabilizer is one or more than two of trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, triphenyl phosphite and tri-m-toluyl phosphite.
5. The method of claim 1, wherein: the temperature of the esterification reaction is 200-240 ℃, the pressure is controlled to be 0-0.5 MPaG, the stirring speed is 50-200 rpm, and the reaction time is 1-4 h.
6. The method of claim 1, wherein: the temperature of the pre-polycondensation reaction is 220-260 ℃, the pressure is controlled to be 5-50 kPaA, the stirring speed is 50-200 rpm, and the reaction time is 0.5-2 h.
7. The method of claim 1, wherein: the temperature of the post-polycondensation reaction is 220-300 ℃, the pressure is controlled at 50 Pa-1 kPa, and the reaction time is 0.1-1 h.
8. The method of claim 1, wherein: the esterification reaction and the pre-polycondensation reaction are carried out in a reaction kettle, and the post-polycondensation reaction is carried out in a horizontal polycondensation kettle, a falling film evaporator or a packed tower.
9. The method of claim 3, wherein: the specific process of polyester synthesis is as follows:
(1) nitrogen replacement is carried out on each device before reaction;
(2) adding terephthalic acid and dihydric alcohol into an esterification reaction kettle according to a certain proportion, simultaneously adding an esterification catalyst to start reaction, and ending the esterification reaction when the water yield reaches 90% of the theoretical amount;
(3) feeding the esterification reaction liquid into a pre-polycondensation reaction kettle, adding a polymerization catalyst, controlling the reaction pressure by a vacuum pump, and ending the pre-polycondensation when the liquid output reaches 90% of the mass of the excessive dihydric alcohol;
(4) and (3) feeding the pre-polycondensation reaction liquid into a post-polycondensation reactor, adding a trace amount of stabilizer, controlling the reaction pressure through a vacuum pump, and finishing the reaction and discharging.
10. The method of claim 3, wherein: the specific process of polyester synthesis is as follows:
(1) nitrogen replacement is carried out on each device before reaction;
(2) adding terephthalic acid and dihydric alcohol into an esterification reaction kettle according to a certain proportion, simultaneously adding a composite catalyst to start reaction, and ending the esterification reaction when the water yield reaches 90% of the theoretical amount;
(3) feeding the esterification reaction liquid into a pre-polycondensation reaction kettle, controlling the reaction pressure by a vacuum pump, and ending the pre-polycondensation when the liquid output reaches 90% of the mass of the excessive dihydric alcohol;
(4) and (4) enabling the pre-polycondensation reaction liquid to enter a post-polycondensation reactor, controlling the reaction pressure through a vacuum pump, and discharging after the reaction is finished.
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