CN117801235A - Preparation method of poly (butylene succinate) - Google Patents

Preparation method of poly (butylene succinate) Download PDF

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Publication number
CN117801235A
CN117801235A CN202311761228.8A CN202311761228A CN117801235A CN 117801235 A CN117801235 A CN 117801235A CN 202311761228 A CN202311761228 A CN 202311761228A CN 117801235 A CN117801235 A CN 117801235A
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butanediol
methoxytetrahydrofuran
reaction
furyl
tetrahydro
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Inventor
丁可
刘英瑞
刘运海
胡江林
赵欣
郭凤娇
史意胜
蒋玉鑫
杨洋
陈永
宋延方
高杭
陈伟
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Wanhua Chemical Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/85Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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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 discloses a preparation method of polybutylene succinate. The method comprises the following steps: 1) 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol are contained in the raw material 1, 4-butanediol in a total amount of 0.01-0.5wt%, and the mass ratio of 2-methoxytetrahydrofuran to 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol is (0.3-5): 1; 2) The 1, 4-butanediol is used as a raw material, and is subjected to esterification polycondensation reaction with succinic acid in the presence of a catalyst to generate the poly (butylene succinate). The invention improves the molecular weight and distribution of PBS products and improves the mechanical property and thermal property of PBS products.

Description

Preparation method of poly (butylene succinate)
Technical Field
The invention relates to preparation of a high polymer material, in particular to a preparation method of polybutylene succinate.
Background
Polybutylene succinate (PBS) is a copolymer of succinic acid and butanediol, has excellent biodegradability, and has strong application potential in the field of food contact materials such as disposable cutlery boxes, straws and the like. However, PBS has not been applied on a large scale until now, and besides the fact that the cost of raw materials is relatively high compared with that of the traditional polyolefin materials, the processing temperature is relatively low, and finally the PBS has low molecular weight, low viscosity and mechanical properties which cannot be compared with those of general plastics. In addition, the application scenes of disposable cutlery boxes, straws and the like require that the PBS material has excellent heat distortion temperature.
Therefore, how to increase the molecular weight, mechanical properties and thermal stability of PBS is a problem to be solved.
Patent CN1424339a discloses a process for preparing PBS using benzenesulfonic acid, tin oxide, antimony trioxide, cadmium acetate, titanate or any mixture of two or more thereof as catalyst, but the molecular weight of the product is only up to 13.7 tens of thousands, and the Heat Distortion Temperature (HDT) of the product is not improved.
Patent CN101935391B discloses a preparation method of high molecular weight aliphatic polyester, which uses aliphatic diacid diester and aliphatic diol as raw materials to perform melt polycondensation, so that aliphatic polyester with weight average molecular weight of 5-25 ten thousand and molecular weight distribution coefficient of 1.9-2.2 can be obtained, but the method has the disadvantages of long reaction time, low catalyst activity and wide molecular weight distribution, which can reduce the heat distortion temperature of the polyester and affect the application of the product in catering industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of polybutylene succinate.
The preparation method of the polybutylene succinate comprises the following steps:
1) 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol are contained in the raw material 1, 4-butanediol in a total amount of 0.01-0.5wt%, and the mass ratio of 2-methoxytetrahydrofuran to 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol is (0.3-5): 1;
2) The 1, 4-butanediol is used as a raw material, and is subjected to esterification polycondensation reaction with succinic acid in the presence of a catalyst to generate the poly (butylene succinate).
As a preferred embodiment of the present invention, in step 1), the raw material 1, 4-butanediol is controlled to contain 0.02 to 0.25% by weight of 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol in total, and the mass ratio of 2-methoxytetrahydrofuran to 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol is (1 to 3): 1.
In the invention, the method for controlling the content and the proportion of 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol (TOBO) in the raw material 1, 4-butanediol can be directly added, or the raw material 1, 4-butanediol can be pretreated in a reaction rectification mode, so that a certain amount of 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol which is inevitably present in the raw material 1, 4-butanediol is converted into 2-methoxytetrahydrofuran meeting the limiting condition, or the two control modes can be combined, and the method can be simply adjusted according to the disclosure information of the invention for a person skilled in the art, so that the method does not play a limiting role in any form.
As a specific example of the reactive distillation, for example, 1, 4-butanediol containing 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol and methanol are mixed and subjected to the reactive distillation, and the catalyst used is, for example, a solid acid catalyst, preferably one or more of molecular sieves, cationic resins, solid superacids, more preferably the cationic resins Rogowski Amberlite35 and/or Dandelion pearl DA330, to such an extent that the contents of 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol in 1, 4-butanediol are controlled within the above-defined ranges. In some special cases, for example, when the TOBO content in 1, 4-butanediol is too low, a corresponding amount of TOBO can be added.
In the long-term study of the correlation between the performance and the production condition of PBS, the inventor finds that the molecular weight of PBS is improved to a certain extent by controlling the content of monohydroxy impurity TOBO in the raw material, and simultaneously, the introduction of a certain amount of 2-methoxytetrahydrofuran is more beneficial to further promoting the increase of the molecular weight of PBS, and the decomposition of the PBS under the polycondensation reaction working condition is presumed to generate reactive substances which can serve as a chain extender, so that the invention preferably converts a certain amount of TOBO into 2-methoxytetrahydrofuran by adding methanol under the condition of reactive rectification so as to improve the molecular weight of the product from the source in the high molecular synthesis stage. However, in the deep research, the TOBO content in the 1, 4-butanediol is not too low, otherwise the mechanical property and the thermal stability of the PBS material are lost, and particularly, when the total amount of the TOBO and the 2-methoxytetrahydrofuran in the 1, 4-butanediol is controlled to be more than 0.01wt percent and less than 0.5wt percent and the mass ratio of the 2-methoxytetrahydrofuran to the TOBO is more than 0.3:1 and less than 5:1, the mechanical property and the thermal stability of the product are obviously improved, so that the invention is completed.
As a preferred embodiment of the present invention, the molar ratio of succinic acid to 1, 4-butanediol is 1 (1.1-1.5), preferably 1 (1.1-1.3).
As a preferable scheme of the invention, the catalyst comprises a main catalyst and an auxiliary agent, wherein the main catalyst is titanate, and the auxiliary agent is a phosphorus-containing compound;
preferably, the main catalyst is one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate and tetramethyl titanate;
preferably, the auxiliary agent is one or more of trimethyl phosphate, triethyl phosphate and triphenyl phosphate.
As a preferable scheme of the invention, the dosage of the main catalyst is 50-300 ppm, calculated by the sum of the mass of the metallic titanium relative to the raw materials succinic acid and 1, 4-butanediol;
preferably, the amount of the auxiliary agent is 10-100ppm, calculated as the sum of the mass of phosphorus element relative to the raw materials succinic acid and 1, 4-butanediol.
As a preferable scheme of the invention, the reaction process is divided into two stages of esterification reaction and polycondensation reaction; wherein the esterification reaction temperature is 180-250 ℃, and the content of byproduct water reaches more than 95% of theoretical water yield to serve as a reaction end point;
the polycondensation reaction is carried out by vacuumizing to 1000-30000PaA for 10-60min, vacuumizing to below 100PaA, heating to 220-260 deg.C, and reacting for 60-200min.
The research of the invention discovers that the content of 2-methoxytetrahydrofuran and TOBO in the 1, 4-butanediol raw material is controlled within a certain range, and the molecular weight and the distribution of PBS products can be improved and the mechanical property and the thermal property of the PBS products can be improved by adjusting the content of 2-methoxytetrahydrofuran and TOBO in a certain proportion.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The sources of the reagent raw materials used in the examples and comparative examples of the present invention are shown in the following table 1, and the remaining reagent raw materials are all common commercial products unless otherwise specified:
table 1 information on main raw materials used in examples
Reagent(s) Manufacturing factories Specification of specification
Trimethyl phosphate Alatine 98%
BDO Xinjiang Meike, dalian chemistry Industrial grade
Tetrabutyl titanate Alatine 98%
Succinic acid Shandong flying chemical industry Superior product
DA330 Dandong pearl --
Amberlite35 Rogowski --
Methanol Alatine AR
TOBO Kamaier 97%
In the present invention, the content of 1, 4-butanediol as a raw material and TOBO and 2-methoxytetrahydrofuran therein is measured by gas chromatography. The gas chromatographic analysis was carried out according to 30m DB-WAX, ID.:0.32mm, FD.:0.25 μm;50-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400mL/min; sample injection amount: 0.2. Mu.L.
In the present invention, the basic physical properties of the resin were tested by the following method:
a) Relative molecular mass: the polymer was tested for relative molecular mass using Waters gel chromatography with chloroform as the mobile phase and at an outflow rate of 1mL/min at 40℃and a narrow distribution of polystyrene as the standard.
b) Mechanical properties: tensile strength and elongation at break were measured using an Instron 5966 universal tester from Instron Inc. (see ISO 527 method).
c) Heat distortion temperature: the heat distortion and Vicat softening point temperature measurement are carried out by adopting a Hua plastic HDT/V-1103.
The following examples 1-5, comparative examples 1-3 were used to provide 1, 4-Butanediol (BDO) for PBS production:
example 1
3*3 theta ring packing and 20ml dandong pearl DA330 resin are added into a 50cm long rectification column, and the reaction rectification conditions are as follows: the temperature of the tower kettle is controlled at 150 ℃, the reflux ratio is 3:1, and the pressure is normal pressure. Outsourced technical BDO (TOBO content 0.04 wt%) is continuously fed into a reactive rectifying tower from the tower top, the feeding rate is 60g/h, the methanol is fed into the tower bottom, the feeding amount is 30g/h, after the reaction in the rectifying tower, the excessive methanol is extracted from the tower top, and BDO-1 is obtained from the tower bottom, wherein the TOBO content and 2-methoxytetrahydrofuran content are respectively 0.02wt% and 0.01wt%.
Example 2
3*3 theta ring packing and 20ml dandong pearl DA330 resin are added into a 50cm long rectification column, and the reaction rectification conditions are as follows: the temperature of the tower kettle is controlled at 145 ℃, the reflux ratio is 5:1, and the pressure is normal pressure. Outsourced technical-grade BDO (TOBO content 0.14 wt%) is continuously fed into a reactive rectifying tower from the tower top, the feeding rate is 40g/h, the methanol is fed into the tower bottom, the feeding rate is 60g/h, after the reaction in the rectifying tower, the excessive methanol is extracted from the tower top, BDO-2 is obtained from the tower bottom, wherein the TOBO content is 0.04wt% and the 2-methoxytetrahydrofuran content is 0.07wt%.
Example 3
3*3 theta ring packing and 20ml dandong pearl DA330 resin are added into a 50cm long rectification column, and the reaction rectification conditions are as follows: the temperature of the tower kettle is controlled at 155 ℃, the reflux ratio is 5:1, and the pressure is normal pressure. To commercially available technical grade BDO (TOBO content 0.14 wt%) was added TOBO to give a BDO reaction rectification stock solution of 0.29wt% TOBO. The BDO (TOBO content 0.29 wt%) was continuously fed into a reactive rectifying column from the top of the column, the feed rate was 60g/h, methanol was fed into the bottom of the column, the feed rate was 60g/h, after the reaction in the rectifying column, the excess methanol was taken out from the top of the column, BDO-3 was obtained in the bottom of the column, wherein the TOBO content was 0.11wt% and 2-methoxytetrahydrofuran was 0.12wt%.
Example 4
3*3 theta ring packing and 20ml dandong pearl DA330 resin are added into a 50cm long rectification column, and the reaction rectification conditions are as follows: the temperature of the tower kettle is controlled at 155 ℃, the reflux ratio is 5:1, and the pressure is normal pressure. To commercially available technical grade BDO (TOBO content 0.14 wt%) was added TOBO to give a BDO reaction rectification stock solution of 0.59wt% TOBO. The BDO continuously enters a reactive rectifying tower from the top of the tower, the feeding rate is 40g/h, methanol enters from the bottom of the tower, the feeding amount is 60g/h, after the reaction in the rectifying tower, the excessive methanol is extracted from the top of the tower, and BDO-4 is obtained from the bottom of the tower, wherein the TOBO content is 0.15wt% and the 2-methoxytetrahydrofuran content is 0.27wt%.
Comparative example 1
Outsourced technical grade BDO (TOBO content 0.14 wt%) was purified by rectification under the following conditions: the column plate number is 50, the reflux ratio is 20:1, the temperature of a column bottom is 148 ℃, the pressure is 2kPaA, and a refined BDO product BDO-5 is obtained from the column top, wherein the TOBO content is 0.005 weight percent.
Comparative example 2
Commercial grade BDO (TOBO content 0.14 wt%) was directly used as starting material and was designated BDO-6.
Comparative example 3
3*3 theta ring packing and 20ml dandong pearl DA330 resin are added into a 50cm long rectification column, and the reaction rectification conditions are as follows: the temperature of the tower kettle is controlled at 155 ℃, the reflux ratio is 5:1, and the pressure is normal pressure. Outsourcing industrial BDO (TOBO content 0.14 wt%) continuously enters a reactive rectifying tower from the tower top, the feeding rate is 10g/h, methanol enters from the tower bottom, the feeding amount is 60g/h, after the reaction in the rectifying tower, excessive methanol is extracted from the tower top, BDO-7 is obtained from the tower bottom, wherein the TOBO content is 0.01wt% and the 2-methoxytetrahydrofuran content is 0.08wt%.
The following examples 5-9 and comparative examples 4-6 were used to prepare different PBS resins, respectively:
example 5
10mol of succinic acid, 15mol of BDO-1, 3.67g of tetrabutyl titanate and 0.78g of trimethyl phosphate are added into a 5L polyester kettle, the kettle is kept at normal pressure, stirring is carried out at a constant speed of 100rpm, the temperature is increased to 150 ℃ to start the reaction, the temperature is gradually increased to 250 ℃ within 1h, and the esterification process is completed when the amount of distilled byproduct water in the reaction kettle reaches 95% of the theoretical water yield. Gradually vacuumizing the reaction kettle to 15000PaA for 50min, gradually vacuumizing to 90PaA, heating to 220 ℃ and maintaining, performing polycondensation reaction for 200min to obtain polymer melt, and performing water-cooling granulation to obtain a resin product. The product index is shown in table 1 below.
Example 6
10mol of succinic acid, 1.83g of BDO-2 13mol of tetrabutyl titanate and 0.23g of trimethyl phosphate are added into a 5L polyester kettle, the inside of the kettle is kept at normal pressure, stirring is carried out at a constant speed of 100rpm, the temperature is increased to 150 ℃ to start the reaction, the temperature is gradually increased to 250 ℃ within 1h, and the esterification process is completed when the amount of distilled byproduct water in the reaction kettle reaches 95% of the theoretical water yield. Gradually vacuumizing the reaction kettle to 5000PaA for 30min, gradually vacuumizing to 80PaA, heating to 245 ℃ and maintaining, performing polycondensation reaction for 150min to obtain a polymer melt, and performing water-cooling granulation to obtain a resin product. The product index is shown in table 1 below.
Example 7
10mol of succinic acid, 12mol of BDO-3, 1.83g of tetrabutyl titanate and 0.23g of trimethyl phosphate are added into a 5L polyester kettle, the kettle is kept at normal pressure, stirring is carried out at a constant speed of 100rpm, the temperature is increased to 150 ℃ to start the reaction, the temperature is gradually increased to 240 ℃ within 1h, and the esterification process is completed when the amount of distilled byproduct water in the reaction kettle reaches 95% of the theoretical water yield. Gradually vacuumizing the reaction kettle to 4000PaA for 30min, gradually vacuumizing to 90PaA, heating to 250 ℃ and maintaining, performing polycondensation reaction for 150min to obtain a polymer melt, and performing water-cooling granulation to obtain a resin product. The product index is shown in table 1 below.
Example 8
10mol of succinic acid, 1.83g of BDO-3 11mol of tetrabutyl titanate and 0.46g of trimethyl phosphate are added into a 5L polyester kettle, normal pressure is kept in the kettle, stirring is carried out at a constant speed of 100rpm, the temperature is increased to 150 ℃, the reaction is started, the temperature is gradually increased to 240 ℃ in 1h, and the esterification process is completed when the amount of distilled byproduct water in the reaction kettle reaches 95% of the theoretical water yield. Gradually vacuumizing the reaction kettle to 6000PaA for 30min, gradually vacuumizing to 90PaA, heating to 250 ℃ and maintaining, performing polycondensation reaction for 100min to obtain polymer melt, and performing water-cooling granulation to obtain the product. The product index is shown in table 1 below.
Example 9
10mol of succinic acid, 1.83g of BDO-4 12mol of tetrabutyl titanate and 0.23g of trimethyl phosphate are added into a 5L polyester kettle, normal pressure is kept in the kettle, stirring is carried out at a constant speed of 100rpm, the temperature is increased to 150 ℃, the reaction is started, the temperature is gradually increased to 240 ℃ within 1h, and the esterification process is completed when the amount of distilled byproduct water in the reaction kettle reaches 95% of the theoretical water yield. Gradually vacuumizing the reaction kettle to 4000PaA for 30min, gradually vacuumizing to 90PaA, heating to 250 ℃ and maintaining, performing polycondensation reaction for 150min to obtain polymer melt, and performing water-cooling granulation to obtain the product. The product index is shown in table 1 below.
Comparative example 4
PBS was prepared in substantially the same manner as in example 6, except that BDO-1 was replaced with BDO-5. The product index of the obtained resin is shown in table 1 below.
Comparative example 5
PBS was prepared in substantially the same manner as in example 7, except that BDO-1 was replaced with BDO-6. The product index of the obtained resin is shown in table 1 below.
Comparative example 6
PBS was prepared in substantially the same manner as in example 8, except that BDO-1 was replaced with BDO-7. The product index of the obtained resin is shown in table 2 below.
TABLE 2 product index of PBS resin
Molecular weight g/mol Mw/Mn Tensile Strength/MPa Elongation at break/% HDT/℃
Example 5 13.2*10 5 1.95 36.0 191 95.1
Example 6 13.9*10 5 1.92 36.4 198 95.5
Example 7 14.1*10 5 1.90 36.3 194 95.6
Example 8 13.8*10 5 1.94 35.9 196 95.3
Comparative example 4 114.4*10 5 2.32 31.8 134 89.5
Comparative example 5 8.8*10 5 2.43 32.5 164 92.6
Comparative example 6 10.9*10 5 2.28 32.2 141 91.3
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (6)

1. The preparation method of the polybutylene succinate is characterized by comprising the following steps of:
1) 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol are contained in the raw material 1, 4-butanediol in a total amount of 0.01-0.5wt%, and the mass ratio of 2-methoxytetrahydrofuran to 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol is (0.3-5): 1;
2) The 1, 4-butanediol is used as a raw material, and is subjected to esterification polycondensation reaction with succinic acid in the presence of a catalyst to generate the poly (butylene succinate).
2. The method for producing polybutylene succinate according to claim 1, wherein in step 1), the total amount of 2-methoxytetrahydrofuran and 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol contained in the raw material 1, 4-butanediol is controlled to be 0.02 to 0.25% by weight, and the mass ratio of 2-methoxytetrahydrofuran to 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol is controlled to be (1-3): 1.
3. The process for the preparation of polybutylene succinate according to claim 1 or 2, characterized in that the molar ratio of succinic acid to 1, 4-butanediol is 1 (1.1-1.5), preferably 1 (1.1-1.3).
4. The method for preparing polybutylene succinate according to claim 3, wherein the catalyst comprises a main catalyst and an auxiliary agent, wherein the main catalyst is titanate, and the auxiliary agent is a phosphorus-containing compound;
preferably, the main catalyst is one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate and tetramethyl titanate;
preferably, the auxiliary agent is one or more of trimethyl phosphate, triethyl phosphate and triphenyl phosphate.
5. The method for producing polybutylene succinate according to claim 4, wherein the amount of the main catalyst is 50 to 300ppm based on the sum of the mass of metallic titanium relative to the raw materials succinic acid and 1, 4-butanediol;
preferably, the amount of the auxiliary agent is 10-100ppm, calculated as the sum of the mass of phosphorus element relative to the raw materials succinic acid and 1, 4-butanediol.
6. The method for producing polybutylene succinate according to any one of claims 1 to 5, wherein the reaction process is divided into two stages of esterification reaction and polycondensation reaction; wherein the esterification reaction temperature is 180-250 ℃, and the content of byproduct water reaches more than 95% of theoretical water yield to serve as a reaction end point;
the polycondensation reaction is carried out by vacuumizing to 1000-30000PaA for 10-60min, vacuumizing to below 100PaA, heating to 220-260 deg.C, and reacting for 60-200min.
CN202311761228.8A 2023-12-20 2023-12-20 Preparation method of poly (butylene succinate) Pending CN117801235A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116178681A (en) * 2023-02-01 2023-05-30 珠海金发生物材料有限公司 Polybutylene succinate resin and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116178681A (en) * 2023-02-01 2023-05-30 珠海金发生物材料有限公司 Polybutylene succinate resin and preparation method thereof
CN116178681B (en) * 2023-02-01 2024-07-16 珠海金发生物材料有限公司 Polybutylene succinate resin and preparation method thereof

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