CN115417982A - Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester - Google Patents
Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester Download PDFInfo
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- CN115417982A CN115417982A CN202211244710.XA CN202211244710A CN115417982A CN 115417982 A CN115417982 A CN 115417982A CN 202211244710 A CN202211244710 A CN 202211244710A CN 115417982 A CN115417982 A CN 115417982A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention relates to a preparation method of poly terephthalic acid-adipic acid-butanediol copolyester (PBAT). The method comprises the following steps: s1: directly adding terephthalic acid, adipic acid and 1, 4-butanediol or preparing into slurry and adding into a reaction kettle, adding a cyclodextrin modified titanium catalyst and then carrying out esterification reaction; s2: and adding an aminosilane coupling agent into the reaction kettle to carry out polycondensation reaction to obtain a polymer melt, and granulating to obtain the poly (terephthalic acid) -adipic acid-butanediol copolyester polymer. The invention develops a hydrolysis-resistant catalyst for effectively regulating and controlling the reaction activity, and prepares the low-acid-value high-color-phase PBAT.
Description
Technical Field
The invention belongs to the field of biodegradable materials, and particularly relates to a preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester.
Background
PBAT is a long-chain aliphatic-aromatic copolyester high polymer material obtained by condensing esterification Products of Terephthalic Acid (PTA), adipic Acid (AA) and 1, 4-Butanediol (BDO), combines the degradability of aliphatic polyester and the mechanical and thermal properties of aromatic polyester, is an important biodegradable material, can effectively solve the environmental problem caused by white pollution, and has great market potential and development space. PBAT slowly degrades under certain conditions to generate polymer fragments with carboxyl and hydroxyl end groups, and then the degradation rate of the polyester is greatly accelerated due to the existence of more end groups, particularly the carboxyl end groups. Finally, the carbon dioxide and the water are changed into carbon dioxide and water through the action of microorganisms. However, this property also results in too rapid degradation in hot and humid environments, and application is greatly limited, and thus the carboxyl end group content must be reduced. The terminal carboxyl is generated generally because the titanium catalyst not only has higher catalytic activity, but also has higher thermal degradation activity, so that more side reactions are generated at the later stage of the polycondensation reaction, the thermal degradation generates the terminal carboxyl, and the color of the product is red.
CN103467713 discloses a low carboxyl biodegradable polyester and a preparation method thereof, wherein the catalytic activity of a titanium catalyst is controlled by using a composite titanium catalyst and adding a chelate having a stabilizing effect at the later stage of an esterification reaction, so as to avoid a side reaction of product degradation caused by the high activity of the catalyst at the later stage of a polycondensation reaction, but the effect is limited, a carboxyl scavenger is still required to be added to reduce the content of terminal carboxyl, and the used carboxyl scavenger is mainly a glycidyl ether compound, so that the boiling point is low, the carboxyl scavenger is easy to be pumped away in the using process, and the utilization rate is low.
CN102007159 describes a method for preparing aliphatic-aromatic biodegradable polyester, which can effectively reduce the acid value of polyester by using chain extender such as isocyanate and adding acid scavenger such as carbodiimide, but the isocyanate has strong toxicity and affects the application of polyester in the food field, and the used acid scavenger such as carbodiimide compound has irritant gas overflow during high temperature processing and using, and affects the environment.
In conclusion, the method has important significance for developing a hydrolysis-resistant catalyst for effectively regulating and controlling the reaction activity and preparing the low-acid-value high-color-phase PBAT.
Disclosure of Invention
The invention provides a preparation method of poly terephthalic acid-adipic acid-butanediol copolyester (PBAT) aiming at the defects in the prior art. The method can effectively reduce the occurrence of side reaction and prepare the PBAT with low acid value and high color phase.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing poly (terephthalic acid-adipic acid-butanediol copolyester) (PBAT), the method comprising the steps of:
s1: respectively adding raw materials of terephthalic acid, adipic acid and 1, 4-butanediol into a reaction kettle or preparing the raw materials into slurry together and then adding the slurry into the reaction kettle, and adding a cyclodextrin modified titanium catalyst to perform esterification reaction;
s2: and adding an aminosilane coupling agent into the reaction kettle for polycondensation reaction to obtain a polymer melt, and granulating to obtain the poly (terephthalic acid) -adipic acid-butanediol copolyester polymer.
According to the invention, the cyclodextrin is used for modifying titanate, various organic compounds can be embedded into the hydrophobic cavity of the cyclodextrin to form an inclusion compound, the characteristics of physical and chemical properties of the inclusion compound are changed, the activity of the titanium at the catalytic center is effectively regulated and controlled, the catalytic action of the titanium on side reactions such as thermal degradation is reduced, and the content of carboxyl at the PBAT end and the value a are effectively reduced. And meanwhile, the PBAT has a branching effect due to the introduction of the polyamino silane coupling agent, the mechanical property of the PBAT is improved, and the compatibility of the PBAT is also improved.
In the present invention, the molar ratio of the sum of terephthalic acid and adipic acid to 1, 4-butanediol in S1 is 1.1 to 1.5, preferably 1.1 to 1; preferably, the molar ratio between terephthalic acid and adipic acid is 0.1 to 0.9, preferably 0.4.
In the invention, the cyclodextrin modified titanium catalyst S1 is a cyclodextrin cavity-enveloped titanium compound; preferably, the cyclodextrin modified titanium catalyst S1 accounts for 0.02-2%, preferably 0.2-1% of the total mass of the terephthalic acid and the adipic acid.
In the invention, the esterification reaction of S1 is carried out at the normal pressure of 180-230 ℃, and the byproduct water is removed.
In the invention, when the total esterification rate of S1 reaches more than 95%, the esterification reaction is finished.
In the invention, the preparation method of the cyclodextrin modified titanium catalyst S1 comprises the following steps:
SS1: adding the carrier and the cyclodextrin into a solvent for reaction;
and SS2: and adding titanate, continuing to react, filtering, and drying to constant weight to obtain the cyclodextrin modified titanium catalyst.
In the invention, the carrier SS1 is one or more of molecular sieve, activated carbon, diatomite and montmorillonite, preferably molecular sieve, more preferably 50-200 mesh molecular sieve.
In the invention, the cyclodextrin of SS1 is cyclodextrin with 6-10D-glucopyranose units, preferably beta-cyclodextrin; preferably, the mass ratio of the carrier to the cyclodextrin is 5:1 to 30:1, preferably 10:1 to 20:1.
in the invention, the solvent of SS1 is one or more of alcohol, ketone and ether, preferably C2-C4 small molecular alcohol, and more preferably ethanol; preferably, the mass ratio of the carrier to the solvent is 1.
In the present invention, the SS1 is reacted at a temperature of 60 to 200 ℃, preferably 100 to 150 ℃ for 1 to 8 hours, preferably 3 to 5 hours.
In the present invention, the titanate of SS2 is Ti (OR) 4 R is alkyl of 1 to 10 carbon atoms, preferably one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate and tetramethyl titanate; preferably, the mass ratio of the titanate to the carrier is 1.
In the invention, the SS2 reaction time is 1 to 8 hours, preferably 3 to 5 hours; the drying temperature is 80-150 ℃, preferably 100-120 ℃.
In the invention, the amino silane coupling agent S2 is one or more of a monoamino silane coupling agent, a diamino silane coupling agent and a triamino silane coupling agent, and preferably the diamino silane coupling agent.
In the invention, the addition amount of the aminosilane coupling agent S2 accounts for 0.001-0.2%, preferably 0.01-0.05% of the total mass of the terephthalic acid and the adipic acid.
In the invention, the polycondensation reaction of S2 is vacuumized twice, the first time is vacuumized to 1000-30,000PaA, and the time lasts for 10-60 min; vacuumizing for the second time to less than 100PaA, and reacting for 60-200 min at constant temperature of 240-265 ℃. The double evacuation process is a common process for the preparation of PBAT, and other non-preferred schemes than the above can also be adopted in the present invention.
Another object of the present invention is to provide a poly (terephthalic acid-adipic acid-butanediol) copolyester.
The poly (terephthalic acid) -adipic acid-butanediol copolyester (PBAT) is prepared by the preparation method of the poly (terephthalic acid) -adipic acid-butanediol copolyester, the content of terminal carboxyl groups of the poly (terephthalic acid) -adipic acid-butanediol copolyester is less than 25mol/t, and a is less than 1.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
(1) According to the cyclodextrin modified titanium catalyst prepared by the invention, the activity of the titanium in the catalytic center is regulated and controlled, so that the occurrence of thermal degradation side reaction is effectively reduced, the terminal carboxyl is effectively reduced, the content of the terminal carboxyl in the product is less than 25mol/t, the hue is improved, the product a is less than 1, and meanwhile, the outer edge of cyclodextrin contains a large number of hydroxyl groups, so that the cyclodextrin modified titanium catalyst has hydrophilicity, can effectively adsorb water molecules generated in the reaction process, and prevents titanate from being hydrolyzed;
(2) According to the invention, an aminosilane coupling agent is added after esterification, the content of the amino is reduced through the reaction of the amino and the terminal carboxyl, the PBAT branching effect is provided, the mechanical property is improved, and the compatibility of the PBAT is also improved.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
Raw materials:
adipic Acid (AA), industrial grade, homan nylon chemical llc;
terephthalic Acid (PTA), industrial grade, permanent petrochemicals limited;
1, 4-Butanediol (BDO), technical grade, xinjiang Makei chemical industries, inc.;
4A molecular sieve, 50 mesh, alatin reagent ltd;
4A molecular sieve, 100 mesh, allatin reagents, inc.;
4A molecular sieves, 200 mesh, allantin reagents, inc.;
diatomaceous earth, median particle size 19.6 microns, alatin reagent ltd;
alpha-cyclodextrin, 98%, allatin reagents, inc.;
beta-cyclodextrin, 98%, aladdin reagent, inc.;
99% methanol, reagent grade, alatin reagent ltd;
99% ethanol, reagent grade, alatin reagent ltd;
98% tetrabutyl titanate, reagent grade, alatin reagent ltd;
98% tetraisopropyl titanate, reagent grade, alatin reagent ltd;
3-aminopropyltrimethoxysilane, 97%, aladdin reagent, inc.;
n- (. Beta. -aminoethyl-. Gamma. -aminopropyl) methyldimethoxysilane, 96%, allantin reagent, inc.
The apparatus and methods used in the present invention are those commonly used in the art, except where specifically indicated.
Adopting a full-automatic acid value detector of a Beijing Xuxin instrument, measuring an acid value, namely a terminal carboxyl content by a model ST-1514: the method is carried out according to the method A in GB/T14190-2008. The mixed solvent is phenol-trichloromethane with the volume ratio of 2. The standard titration solution is potassium hydroxide-benzyl alcohol, the concentration is 0.01mol/L, and the concentration of the bromophenol blue indicator is 0.2%. Sample preparation: 0.5g of the sample was dissolved in 25.00mL of a phenol-chloroform mixed solvent.
The mechanical properties were tested by the following methods: tensile properties were measured using a mechanical tester (Instron 5960) at a tensile rate of 50mm/min. PBAT uses as the evaluation reference the L, a, b color system, where L is the lightness factor and a and b are the number of color measurements. b represents the yellow-blue balance and has very important significance on the color of the polyester, and the lower the value of b, the better the color. The Color (L value, a value and b value) was automatically measured by a Color35 model automatic Color difference meter from BYKGardner.
Catalyst preparation
Example 1
Weighing 5g of diatomite and 1g of alpha-cyclodextrin, dissolving in 250g of methanol, reacting for 8 hours at 60 ℃, adding 0.5g of tetraisopropyl titanate, continuing to react for 1 hour, cooling to room temperature, filtering, and drying at 80 ℃ until the weight is constant to obtain the catalyst A.
Example 2
30g of a 50-mesh 4A molecular sieve and 1g of beta-cyclodextrin are weighed, dissolved in 450g of ethanol, reacted for 2 hours at 200 ℃, added with 0.75g of tetrabutyl titanate, continuously reacted for 8 hours, cooled to room temperature, filtered, and dried at 150 ℃ until the weight is constant, thus obtaining the catalyst B.
Example 3
Weighing 15g of a 200-mesh 4A molecular sieve and 1g of beta-cyclodextrin, dissolving in 375g of ethanol, reacting for 4 hours at 120 ℃, adding 0.6g of tetrabutyl titanate, continuing to react for 4 hours, cooling to room temperature, filtering, and drying at 110 ℃ until the weight is constant to prepare a catalyst C.
Comparative example 1
In contrast to example 3, this comparative example did not use cyclodextrin to modify the titanate.
Weighing 15g of a 100-mesh 4A molecular sieve and 0.6g of tetrabutyl titanate, dissolving in 375g of ethanol, reacting for 4 hours at 120 ℃, cooling to room temperature, filtering, and drying at 110 ℃ until the weight is constant to prepare a catalyst D.
Preparation of polyesters
Example 4
5mol of terephthalic acid, 5mol of adipic acid, 11mol of butanediol and 0.312g of catalyst A are added into a 5L polyester kettle, the kettle is kept at normal pressure, the mixture is stirred at a constant speed of 100rpm, the temperature is raised to 150 ℃ for starting reaction, the temperature is gradually raised to 180 ℃ within 1h, and the esterification process is finished when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Adding 3.12g of 3-aminopropyltrimethoxysilane, gradually vacuumizing the reaction kettle to 30000PaA for 60min, then gradually vacuumizing to 60PaA, heating to 240 ℃ and keeping for polycondensation reaction for 200min to obtain a polymer melt, and water-cooling and granulating to obtain the product.
Example 5
5mol of terephthalic acid, 5mol of adipic acid, 15mol of butanediol and 31.2g of catalyst B are added into a 5L polyester kettle, the kettle is kept at normal pressure, the mixture is stirred at a constant speed of 100rpm, the temperature is raised to 150 ℃, the reaction is started, the temperature is gradually raised to 230 ℃ within 1h, and the esterification process is finished when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Adding 0.0156g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, gradually vacuumizing the reaction kettle to 1000PaA for 20min, then gradually vacuumizing to 60PaA, heating to 265 ℃ and keeping, carrying out polycondensation reaction for 60min to obtain a polymer melt, and carrying out water cooling and granulating to obtain the product.
Example 6
5mol of terephthalic acid, 5mol of adipic acid, 12mol of butanediol and 7.8g of catalyst C are added into a 5L polyester kettle, the kettle is kept at normal pressure, the mixture is stirred at a constant speed of 100rpm, the temperature is raised to 150 ℃ for starting reaction, the temperature is gradually raised to 200 ℃ within 1h, and the esterification process is finished when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Adding 0.468g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, gradually vacuumizing the reaction kettle to 3000PaA for 50min, then gradually vacuumizing to 60PaA, heating to 250 ℃ and keeping, carrying out polycondensation reaction for 150min to obtain a polymer melt, and carrying out water cooling granulation to obtain the product.
Comparative example 2
In contrast to example 6, this comparative example did not add the aminosiloxane coupling agent.
5mol of terephthalic acid, 5mol of adipic acid, 12mol of butanediol and 7.8g of catalyst C are added into a 5L polyester kettle, the kettle is kept at normal pressure, the mixture is stirred at a constant speed of 100rpm, the temperature is raised to 150 ℃ for starting reaction, the temperature is gradually raised to 200 ℃ within 1h, and the esterification process is finished when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Gradually vacuumizing the reaction kettle to 3000PaA for 50min, then gradually vacuumizing to 60PaA, heating to 250 ℃ and keeping, carrying out polycondensation reaction for 150min to obtain a polymer melt, and carrying out water cooling and grain cutting to obtain the product.
Comparative example 3
In contrast to example 6, this comparative example used a catalyst titanate that was not modified with cyclodextrin.
5mol of terephthalic acid, 5mol of adipic acid, 12mol of butanediol and 7.8g of catalyst D are added into a 5L polyester kettle, the kettle is kept at normal pressure, stirred at a constant speed of 100rpm, heated to 150 ℃ for starting reaction, gradually heated to 200 ℃ within 1 hour, and the esterification process is finished when the amount of by-product water distilled out of the reaction kettle reaches 95% of theoretical water yield. Adding 0.468g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, gradually vacuumizing the reaction kettle to 3000PaA for 50min, then gradually vacuumizing to 60PaA, heating to 250 ℃ and keeping, carrying out polycondensation reaction for 150min to obtain a polymer melt, and carrying out water cooling granulation to obtain the product.
Comparative example 4
In contrast to example 6, this comparative example uses titanate as catalyst without addition of an aminosilane coupling agent.
5mol of terephthalic acid, 5mol of adipic acid, 12mol of butanediol and 7.8g of tetrabutyl titanate are added into a 5L polyester kettle, the kettle is kept at normal pressure, the stirring is carried out at a constant speed of 100rpm, the temperature is raised to 150 ℃, the reaction is started, the temperature is gradually raised to 200 ℃ within 1h, and the esterification process is completed when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Gradually vacuumizing the reaction kettle to 3000PaA for 50min, then gradually vacuumizing to 60PaA, heating to 250 ℃ and keeping for polycondensation reaction for 150min to obtain a polymer melt, and water-cooling and granulating to obtain the product.
TABLE 1PBAT Properties
| Group of | Carboxyl end group content/mol/t | L | a | b | Tensile strength/MPa |
| Example 4 | 23 | 84 | 0.3 | 4.6 | 43 |
| Example 5 | 21 | 87 | -0.1 | 3.7 | 47 |
| Example 6 | 15 | 89 | -1.4 | 2.1 | 55 |
| Comparative example 2 | 34 | 78 | 2.4 | 6.3 | 20 |
| Comparative example 3 | 45 | 71 | 3.1 | 7.9 | 24 |
| Comparative example 4 | 57 | 65 | 5.3 | 8.4 | 17 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (7)
1. A method for preparing poly (terephthalic acid) -adipic acid-butanediol copolyester, characterized in that the method comprises the following steps:
s1: respectively adding raw materials of terephthalic acid, adipic acid and 1, 4-butanediol into a reaction kettle or preparing the raw materials into slurry together and then adding the slurry into the reaction kettle, and adding a cyclodextrin modified titanium catalyst to perform esterification reaction;
s2: and adding an aminosilane coupling agent into the reaction kettle to carry out polycondensation reaction to obtain a polymer melt, and granulating to obtain the poly (terephthalic acid) -adipic acid-butanediol copolyester polymer.
2. The method for preparing poly (terephthalic-adipic acid-butanediol) copolyester according to claim 1, wherein the molar ratio of the sum of terephthalic acid and adipic acid to 1, 4-butanediol in the S1 is 1.1-1.5, preferably 1;
preferably, the molar ratio between terephthalic acid and adipic acid is 0.1 to 0.9, preferably 0.4;
and/or the cyclodextrin modified titanium catalyst S1 is a cyclodextrin cavity-enveloped titanium compound;
preferably, the cyclodextrin modified titanium catalyst S1 accounts for 0.02-2% of the total mass of the terephthalic acid and the adipic acid, and preferably accounts for 0.2-1%;
and/or, carrying out esterification reaction on the S1 at the normal pressure of 180-230 ℃, and removing byproduct water;
and/or when the total esterification rate of S1 reaches more than 95 percent, finishing the esterification reaction.
3. The method for preparing poly (terephthalic acid-adipic acid-butanediol) copolyester according to claim 1 or 2, wherein the method for preparing the cyclodextrin modified titanium catalyst S1 comprises the following steps:
and (4) SS1: adding the carrier and the cyclodextrin into a solvent for reaction;
and (4) SS2: and adding titanate, continuing to react, filtering, and drying to constant weight to obtain the cyclodextrin modified titanium catalyst.
4. The method for preparing poly (terephthalic acid-adipic acid-butanediol) copolyester according to claim 3, wherein the carrier SS1 is one or more of molecular sieve, activated carbon, diatomite and montmorillonite, preferably molecular sieve, more preferably 50-200 mesh molecular sieve;
and/or the cyclodextrin of SS1 is cyclodextrin with 6-10D-glucopyranose units, preferably beta-cyclodextrin;
preferably, the mass ratio of the carrier to the cyclodextrin is 5:1 to 30:1, preferably 10:1 to 20:1;
and/or the solvent of SS1 is one or more of alcohol, ketone and ether, preferably C2-C4 small molecular alcohol, more preferably ethanol;
preferably, the mass ratio of the carrier to the solvent is 1;
and/or the SS1 reaction temperature is 60-200 ℃, preferably 100-150 ℃, and the reaction time is 1-8 hours, preferably 3-5 hours.
5. The method of claim 3, wherein the titanate of SS2 is Ti (OR) 4 R is alkyl of 1 to 10 carbon atoms, preferably one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate and tetramethyl titanate;
preferably, the mass ratio of the titanate to the carrier is 1;
and/or the SS2 reaction time is 1 to 8 hours, preferably 3 to 5 hours; the drying temperature is 80-150 ℃, preferably 100-120 ℃.
6. The method for preparing poly (terephthalic acid-adipic acid-butanediol) copolyester according to claim 1, wherein S2 the aminosilane coupling agent is one or more of monoamino silane coupling agent, diamino silane coupling agent and triamino silane coupling agent, preferably diamino silane coupling agent;
and/or, the addition amount of the amino silane coupling agent S2 accounts for 0.001-0.2 percent of the total mass of the terephthalic acid and the adipic acid, and preferably 0.01-0.05 percent;
and/or, the polycondensation reaction of S2 is vacuumized twice, the first time is vacuumized to 1000-30,000PaA, and the time lasts for 10-60 min; vacuumizing for the second time to less than 100PaA, and reacting for 60-200 min at constant temperature of 240-265 ℃.
7. A poly (terephthalic acid-adipic acid-butanediol) copolyester, prepared by the method for preparing the poly (terephthalic acid-adipic acid-butanediol) copolyester as claimed in any one of claims 1 to 6, wherein the content of carboxyl end groups of the poly (terephthalic acid-adipic acid-butanediol) copolyester is less than 25mol/t, and a is less than 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117417514A (en) * | 2023-12-18 | 2024-01-19 | 康辉新材料科技有限公司 | Anthracene-2, 6-dicarboxylic acid modified PBAT degradation material, preparation method and application thereof |
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| DE19614441A1 (en) * | 1996-04-12 | 1997-10-16 | Basf Ag | Poly:urethane moulding materials |
| CN103665351A (en) * | 2013-11-29 | 2014-03-26 | 金发科技股份有限公司 | Poly-terephthalic acid cyclohexanedimethanol /butanediol copolyester, and preparation and application thereof |
| CN113861394A (en) * | 2021-10-13 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19614441A1 (en) * | 1996-04-12 | 1997-10-16 | Basf Ag | Poly:urethane moulding materials |
| CN103665351A (en) * | 2013-11-29 | 2014-03-26 | 金发科技股份有限公司 | Poly-terephthalic acid cyclohexanedimethanol /butanediol copolyester, and preparation and application thereof |
| CN113861394A (en) * | 2021-10-13 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117417514A (en) * | 2023-12-18 | 2024-01-19 | 康辉新材料科技有限公司 | Anthracene-2, 6-dicarboxylic acid modified PBAT degradation material, preparation method and application thereof |
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