CN116144004A - Heterogeneous titanium catalyst for PBAT polymerization and preparation method and application thereof - Google Patents
Heterogeneous titanium catalyst for PBAT polymerization and preparation method and application thereof Download PDFInfo
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- CN116144004A CN116144004A CN202310173741.9A CN202310173741A CN116144004A CN 116144004 A CN116144004 A CN 116144004A CN 202310173741 A CN202310173741 A CN 202310173741A CN 116144004 A CN116144004 A CN 116144004A
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- 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
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- 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
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- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a heterogeneous titanium catalyst for PBAT polymerization, a preparation method and application thereof, wherein the heterogeneous titanium catalyst comprises a titanium compound, a metal salt and an organic compound containing active hydrogen; the molar ratio of the active hydrogen functional group of the organic compound containing active hydrogen to the titanium compound is 0.3-30; the molar ratio of the metal salt to the titanium compound is 0.2-20; the organic compound containing active hydrogen is selected from C containing one or more of hydroxyl, phenolic hydroxyl, carboxyl, amino, mercapto, phosphate and sulfo 1 ～C 30 Branched or straight chain alkanes, cycloalkanes, arenes, alkenes, alkynes or heterocyles; the titanium compound has the general formula of Ti (OR) 4 OR Ti (OR) 2 Cl 2 A compound; the metal salt is selected from one or more of magnesium, lanthanum, cerium, zinc, zirconium, sodium, potassium, calcium, lithium and hydrate thereof. The heterogeneous titanium-based catalyst of the present invention has high activity under relatively low temperature conditions.
Description
Technical Field
The invention belongs to the technical field of polyester synthesis, and particularly relates to a heterogeneous titanium catalyst for PBAT polymerization, and a preparation method and application thereof.
Background
The aliphatic-aromatic copolyester has excellent mechanical property and biodegradability, is one of good substitutes of traditional plastics and a treatment method for solving the environmental problem caused by the good substitutes, wherein poly (butylene adipate-butylene terephthalate) (PBAT) is thermoplastic biodegradable plastics, and has the characteristics of polybutyl acrylate (PBA) and polybutylene terephthalate (PBT) due to a flexible aliphatic chain segment and a rigid aromatic chain segment, so that the aliphatic-aromatic copolyester has better ductility and elongation at break, better heat resistance and impact resistance, is one of the best biodegradable materials with performance and cost advantages in the existing biodegradable high polymer materials, and is the third biodegradable plastic after starch-based plastics and polylactic acid. The polymerization mode of the PBAT is a direct esterification method (PTA method) or a transesterification method (dimethyl terephthalate, DMT method). Wherein the PTA method takes terephthalic acid (PTA), adipic Acid (AA) and 1, 4-Butanediol (BDO) as raw materials, and a certain amount of catalyst and proper reaction temperature are used for esterification and polycondensation to synthesize PBAT; the DMT method is to put dimethyl terephthalate (DMT), 1, 4-Butanediol (BDO) and a proper amount of catalyst into a reaction kettle, distill methanol to a theoretical amount, put a certain amount of Adipic Acid (AA) into the reaction kettle, distill corresponding water, then finish esterification, and then obtain PBAT through polycondensation.
In the industrial production of polyesters, the catalyst is a key point concerning the quality and performance of the polymerization product. At present, catalysts commonly used in the polyester synthesis process, such as tetrabutyl titanate (TBOT) and antimony trioxide (Sb 2 O 3 ) Antimony glycol [ Sb ] 2 (EG) 3 ]Magnesium acetate [ Mg (OAc) 2 ]Etc. Wherein, the high-activity TBOT is used as the most commonly used catalyst of the copolyester PBAT (transesterification method), which can greatly shorten the polymerization time and improve the reaction rate. However, in the direct esterification method (PTA method), the added catalyst content is excessive, so that byproducts are more in the polymerization process, and the molecular weight of the product is lower. TBOT is easy to hydrolyze, and the water is strictly controlled when the TBOT is put into a reaction kettle, but the water generated by the esterification reaction is inevitably deactivated. Furthermore, in the synthesis of PBAT, 1, 4-butanediol, on the one hand(BDO) tetrahydrofuran is extremely easily produced in the reaction, and high temperature and high pressure promote the progress of this reaction; on the other hand, the carboxyl groups in terephthalic acid (PTA) also accelerate BDO dehydration to tetrahydrofuran. During PBAT synthesis, a catalyst which has higher activity at a lower temperature and can inhibit side reactions of tetrahydrofuran as much as possible should be selected, so that the development of an efficient and high-selectivity environment-friendly novel catalyst for PBAT polymerization has important significance.
Disclosure of Invention
Based on the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide a heterogeneous titanium-based catalyst for PBAT polymerization satisfying one or more of the above-mentioned needs, and a method for preparing and using the same.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a heterogeneous titanium catalyst for PBAT polymerization comprises a titanium compound, a metal salt and an organic compound containing active hydrogen;
wherein the molar ratio of the active hydrogen functional group of the active hydrogen-containing organic compound to the titanium compound is 0.3-30; the molar ratio of the metal salt to the titanium compound is 0.2-20;
the active hydrogen-containing organic compound is C containing one or more of hydroxyl, phenolic hydroxyl, carboxyl, amino, sulfhydryl, phosphate and sulfo 1 ～C 30 Branched or straight chain alkanes, cycloalkanes, arenes, alkenes, alkynes or heterocyles;
the titanium compound has the general formula of Ti (OR) 4 OR Ti (OR) 2 Cl 2 A compound wherein R is selected from C 1 ～C 12 Straight-chain alkyl or branched alkyl of (a).
The metal salt is selected from one or more of magnesium, lanthanum, cerium, zinc, zirconium, sodium, potassium, calcium and lithium metal salts and hydrates thereof.
Preferably, the organic compound containing active hydrogen is selected from the following structures:
preferably, the titanium compound is selected from the following structures:
preferably, the anions of the metal salt are selected from C 6 H 5 COO - 、C 2 O 4 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、CO 3 2- 、HCO 3 - 、C 6 H 5 SO 3 - 、C 6 H 5 O - 、R’SO 3 - 、R’COO - R' is C 1 ～C 10 Branched or straight chain alkanes.
Preferably, the metal salt is selected from the following structures or hydrates thereof:
the invention also provides a preparation method of the heterogeneous titanium catalyst according to any scheme, which comprises the following steps:
(1) Dissolving an organic compound containing active hydrogen in an organic solvent to obtain an organic solution of the organic compound containing active hydrogen; the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, diethylene glycol, glycerol, propylene glycol and butanediol;
(2) Heating an organic solution of an organic compound containing active hydrogen, and adding a titanium compound to enable part of titanate to react with the organic compound containing active hydrogen, wherein the reaction temperature is selected from 30-150 ℃ according to the property of a solvent;
(3) Then dropwise adding an organic solution of metal salt into the system in the step (2), heating the reaction system to obtain precipitate, and reacting part of the metal salt with the rest of titanate at the same reaction temperature as in the step (2) for 0.5-48 h;
(4) Washing, drying and grinding the precipitate obtained in the step (3) to obtain the heterogeneous titanium catalyst.
The invention also provides application of the heterogeneous titanium catalyst in PBAT synthesis, which comprises the following steps:
adding three raw materials of 1, 4-butanediol, terephthalic acid and adipic acid into a reaction vessel for esterification reaction, wherein the esterification temperature is selected from 150-230 ℃, the pressure is selected from 1-3 atmospheres, and the reaction time is selected from 1-20 hours;
after the esterification reaction is finished, carrying out polycondensation reaction, wherein the polycondensation temperature is selected from 230-300 ℃, the reaction pressure is selected from 3-90000 Pa, and the reaction time is selected from 1-24 h;
obtaining PBAT after the polycondensation reaction is finished;
wherein, 1, 4-butanediol: the molar ratio of (terephthalic acid and adipic acid) is 1.2-2.0; terephthalic acid: the molar ratio of adipic acid is 0.1-100; the ratio of the mass of the heterogeneous titanium catalyst to the sum of the mass of the three raw materials is 0.000001-1 wt%.
The invention also provides the use of a heterogeneous titanium-based catalyst according to any one of the preceding schemes, characterized in that it is used for the polymerization of one or more polyacid monomers and one or more polyol monomers to prepare polyesters;
the polyacid monomer has a general formula of HOOC-R1-C0OH, wherein R1 is selected from C1-C23 linear alkyl or branched, unsubstituted or Si, N, O, F substituted alkane, cycloalkane, arene, alkene, alkyne or heterocyclic hydrocarbon;
the general formula of the polyol monomer is a compound of HO-R2-OH, wherein R2 is straight-chain alkyl or branched-chain, unsubstituted or S, si, N, O, F, cl substituted alkane, cycloalkane, arene, alkene, alkyne or heterocyclic hydrocarbon of C1-C26.
Preferably, the polyacid monomer is selected from the following structures:
preferably, the polyol monomer is selected from the following structures:
compared with the prior art, the invention has the beneficial effects that:
(1) By preparing a heterogeneous solid catalyst, the problems of difficult storage, easy hydrolysis, easy coordination coprecipitation with organic ligands and the like of liquid catalysts such as titanate are solved.
(2) The heterogeneous titanium catalyst has the advantages of simple preparation method, good dispersion uniformity, high catalytic activity and reduced catalyst consumption.
(3) Compared with the traditional catalyst, the poly (butylene adipate-butylene terephthalate) (PBAT) prepared by the heterogeneous titanium catalyst has the advantages of better hue, higher molecular weight, higher performance and the like, and the catalyst has high activity under the condition of relatively low temperature, and can catalyze the polymerization of various polyols and polybasic acids to obtain various polyester products.
Detailed Description
The technical scheme of the invention is further explained by the following specific examples.
1. Examples 1 to 43:
weighing a certain amount of organic compound (raw material 3) containing active hydrogen, dissolving in 10 times of volume of organic solvent (depending on the solubility, properly increasing or decreasing), and dissolving in an ultrasonic machine; a certain amount of metal salt (raw material 2) is weighed and dissolved in an organic solvent (the solubility is determined to be proper and can be increased or decreased) with 200 times of the mass, and the mixture is put into an ultrasonic machine for dissolution. And taking out for standby after complete dissolution. The mixed solution of the active hydrogen-containing compound is preheated to a reaction temperature (T), a certain amount of titanium compound (raw material 1) is added, then the mixed solution containing metal salt is added dropwise, and the reaction is carried out for a certain time (T) until precipitation is obtained and the precipitation is complete. The precipitate was separated, washed with water and organic solvent, dried in vacuo and ground to give the product as a white powder. The specific proportions of raw materials 1 to 3 are shown in Table 1.
TABLE 1 raw materials and Process conditions for heterogeneous titanium-based catalysts of examples 1 to 43
a When the mixed solvent is used, the volume ratio of the two solvents is 1:1, but 1:10-10:1, the same applies.
2. Application examples 1-40 preparation of PBAT using heterogeneous titanium-based catalyst
The reaction flow is as follows: terephthalic acid, adipic acid, 1, 4-butanediol and the catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle, esterification reaction is carried out for a certain time at a certain reaction temperature, and water generated by the reaction is discharged through a rectifying device. After the esterification is finished, decompressing and heating to a specific temperature for polycondensation reaction, discharging a product from the bottom of a polymerization reaction kettle for a specific time, cooling in cold water, granulating, drying, and then testing the intrinsic viscosity, the relative molecular weight, the color value and the mechanical property. The catalyst used and the amounts and properties of the PBAT prepared are shown in table 2.
Note that: in application examples 1 to 10, phthalic acid: adipic acid: 1, 4-butanediol = 0.5:0.5:1.4;
in application examples 11 to 20, phthalic acid: adipic acid: 1, 4-butanediol = 0.4:0.6:1.5;
in application examples 21 to 30, phthalic acid: adipic acid: 1, 4-butanediol = 0.8:0.2:1.3;
in application examples 31 to 40, phthalic acid: adipic acid: 1, 4-butanediol = 0.4:0.6:2.0;
in application examples 41 to 50, phthalic acid: adipic acid: 1, 4-butanediol = 0.2:0.8:1.4.
TABLE 2 catalyst and polymerized PBAT Process and Properties
3. Application examples 51-105: catalyzing polymerization of other polybasic acid polyalcohol to obtain polyester.
Since the catalytic activity and the catalytic ability of the catalyst are similar, it is preferable to use the following catalyst as a catalytic model to catalyze the polymerization of the following monomers.
The reaction flow is as follows: a certain amount of polybasic carboxylic acid (monomer 1), polyhydric alcohol (monomer 2) (the ratio of the polyhydric alcohol to the polybasic acid is 1.4:1 according to the corresponding functional group) and the catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle, esterification reaction is carried out for a certain time at a certain reaction temperature, and water generated by the reaction is discharged through a rectifying device. After the esterification is finished, decompressing and heating to a specific temperature for polycondensation reaction, discharging a product from the bottom of a polymerization reaction kettle for a specific time, cooling in cold water, granulating, drying, and then testing the intrinsic viscosity, the relative molecular weight, the color value and the mechanical property. The catalyst used and the properties of the polyester prepared are shown in Table 3.
Table 3 shows the catalyst used and the properties of the prepared polyesters
4. Application examples 106-125: catalyzing polymerization of other polyacid polyols to obtain polyesters
To further increase the degree of polymerization, a suitable amount of polyfunctional monomer is introduced into the catalytic system to increase the degree of polymerization and produce a polyester product having a higher molecular weight. Since the catalytic activity and the catalytic ability of the catalyst are similar, it is preferable to use the following catalyst as a catalytic model to catalyze the polymerization of the following monomers.
The reaction flow is as follows: a certain amount of polycarboxylic acid (monomer 1), polyhydric alcohol (monomer 2), polyfunctional monomer (monomer 3) and the catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle, esterification reaction is carried out for a certain time at a certain reaction temperature, and water generated by the reaction is discharged through a rectifying device. After the esterification is finished, decompressing and heating to a specific temperature for polycondensation reaction, discharging a product from the bottom of a polymerization reaction kettle for a specific time, cooling in cold water, granulating, drying, and then testing the intrinsic viscosity, the relative molecular weight, the color value and the mechanical property. The catalyst used and the properties of the polyester prepared are shown in Table 4.
Table 4 shows the catalyst used and the properties of the prepared polyesters
5. Application examples 126 to 129
The four catalysts are selected below to be compared with the polymerization effect of the existing common catalytic system.
The reaction flow is as follows: terephthalic acid, adipic acid, 1, 4-butanediol and the catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle, esterification reaction is carried out for a certain time at a certain reaction temperature, and water generated by the reaction is discharged through a rectifying device. After the esterification is finished, decompressing and heating to a specific temperature for polycondensation reaction, discharging a product from the bottom of a polymerization reaction kettle for a specific time, cooling in cold water, granulating, drying, and then testing the intrinsic viscosity, the relative molecular weight, the color value and the mechanical property. The catalyst used and the amounts and properties of the PBAT prepared are shown in table 5.
TABLE 5 catalyst and polymerized PBAT Properties
Wherein, the polycondensation temperature of the catalyst Cat.36 is reduced to 230 ℃, and the performance of the PBAT obtained by polymerization is relatively optimal.
Comparative examples 1 to 4:
in conclusion, the heterogeneous titanium catalyst has higher activity at a lower temperature, and products obtained by catalyzing the polymerization of PBAT and other polyesters by using the heterogeneous titanium catalyst have the characteristics of high intrinsic viscosity, high molecular weight, low color value and the like.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.
Claims (10)
1. A heterogeneous titanium catalyst for PBAT polymerization, which is characterized by comprising a titanium compound, a metal salt and an organic compound containing active hydrogen;
wherein the molar ratio of the active hydrogen functional group of the active hydrogen-containing organic compound to the titanium compound is 0.3-30; the molar ratio of the metal salt to the titanium compound is 0.2-20;
the active hydrogen-containing organic compound is C containing one or more of hydroxyl, phenolic hydroxyl, carboxyl, amino, sulfhydryl, phosphate and sulfo 1 ～C 30 Branched or straight chain alkanes, cycloalkanes, arenes, alkenes, alkynes or heterocyles;
the titanium compound has the general formula of Ti (OR) 4 OR Ti (OR) 2 Cl 2 A compound wherein R is selected from C 1 ～C 12 Straight-chain alkyl or branched alkyl of (a).
The metal salt is selected from one or more of magnesium, lanthanum, cerium, zinc, zirconium, sodium, potassium, calcium and lithium metal salts and hydrates thereof.
2. The heterogeneous titanium-based catalyst according to claim 1, wherein the active hydrogen-containing organic compound is selected from the following structures:
3. heterogeneous titanium-based catalyst according to claim 1, characterized in that the titanium compound is selected from the following structures:
4. the heterogeneous titanium-based catalyst according to claim 1, wherein the anion of the metal salt is selected from the group consisting of C 6 H 5 COO - 、C 2 O 4 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、CO 3 2- 、HCO 3 - 、C 6 H 5 SO 3 - 、C 6 H 5 O - 、R’SO 3 - 、R’COO - R' is C 1 ～C 10 Branched or straight chain alkanes.
5. Heterogeneous titanium-based catalyst according to claim 1, characterized in that the metal salt is selected from the following structures or hydrates thereof:
6. the method for producing a heterogeneous titanium-based catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) Dissolving an organic compound containing active hydrogen in an organic solvent to obtain an organic solution of the organic compound containing active hydrogen; the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, diethylene glycol, glycerol, propylene glycol and butanediol;
(2) Heating an organic solution of an organic compound containing active hydrogen, and adding a titanium compound to enable part of titanate to react with the organic compound containing active hydrogen, wherein the reaction temperature is selected from 30-150 ℃ according to the property of a solvent;
(3) Then dropwise adding an organic solution of metal salt into the system in the step (2), heating the reaction system to obtain precipitate, and reacting part of the metal salt with the rest of titanate at the same reaction temperature as in the step (2) for 0.5-48 h;
(4) Washing, drying and grinding the precipitate obtained in the step (3) to obtain the heterogeneous titanium catalyst.
7. Use of a heterogeneous titanium-based catalyst according to any of claims 1-5 for PBAT synthesis, comprising the steps of:
adding three raw materials of 1, 4-butanediol, terephthalic acid and adipic acid into a reaction vessel for esterification reaction, wherein the esterification temperature is selected from 150-230 ℃, the pressure is selected from 1-3 atmospheres, and the reaction time is selected from 1-20 hours;
after the esterification reaction is finished, carrying out polycondensation reaction, wherein the polycondensation temperature is selected from 230-300 ℃, the reaction pressure is selected from 3-90000 Pa, and the reaction time is selected from 1-24 h;
obtaining PBAT after the polycondensation reaction is finished;
wherein, 1, 4-butanediol: the molar ratio of (terephthalic acid and adipic acid) is 1.2-2.0; terephthalic acid: the molar ratio of adipic acid is 0.1-100; the ratio of the mass of the heterogeneous titanium catalyst to the sum of the mass of the three raw materials is 0.000001-1 wt%.
8. Use of a heterogeneous titanium-based catalyst according to any of claims 1-5 for the preparation of polyesters by polymerization of one or more polyacid monomers and one or more polyol monomers;
the polyacid monomer has a general formula of HOOC-R1-C0OH, wherein R1 is selected from C1-C23 linear alkyl or branched, unsubstituted or Si, N, O, F substituted alkane, cycloalkane, arene, alkene, alkyne or heterocyclic hydrocarbon;
the general formula of the polyol monomer is a compound of HO-R2-OH, wherein R2 is straight-chain alkyl or branched-chain, unsubstituted or S, si, N, O, F, cl substituted alkane, cycloalkane, arene, alkene, alkyne or heterocyclic hydrocarbon of C1-C26.
9. The use according to claim 8, wherein the polyacid monomer is selected from the following structures:
10. use according to claim 8, wherein the polyol monomer is selected from the following structures:
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| CN115260470A (en) * | 2022-03-23 | 2022-11-01 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
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| CN115260470A (en) * | 2022-03-23 | 2022-11-01 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
| CN115260470B (en) * | 2022-03-23 | 2023-11-17 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
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