CN116102854B - Preparation method of polybutylene adipate-terephthalate with high lignin content - Google Patents
Preparation method of polybutylene adipate-terephthalate with high lignin content Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
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Abstract
The invention provides a preparation method of polybutylene adipate terephthalate with high lignin content, which comprises the steps of adding a mixture of adipic acid and 1, 4-butanediol into a polycondensation reaction kettle, adding a chain extender, and heating to perform esterification reaction; adding dimethyl terephthalate and 1, 4-butanediol, stirring, adding tetra-n-butyl titanate, and heating to perform transesterification; adding lignin, titanium phosphorus compound, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, heating, melt-polycondensing, cooling, granulating, adding lignin, premixing, transferring to a double-screw extruder, heating, melt-blending, cooling, granulating, and obtaining the polybutylene adipate terephthalate with high lignin content. The overall substitution rate of lignin after the blending process can exceed 60 percent, and good mechanical properties are maintained. The lignin with excellent degradation performance can also ensure the excellent degradation performance of the composite material.
Description
Technical Field
The invention relates to the field of preparation methods of biodegradable plastics, in particular to a preparation method of polybutylene adipate terephthalate with high lignin content.
Background
Polybutylene adipate terephthalate (PBAT) is a thermoplastic polymer with excellent properties, good flexibility, mechanical strength and degradation properties. Along with the continuous increase of the demand of the degradable materials, it is necessary to reduce the raw material cost and the production cost of the PBAT. Lignin is the second largest renewable resource in nature next to cellulose. For a long time, most lignin is discarded as a byproduct of the paper industry or is subjected to low-value utilization such as combustion energy supply. The partial replacement of the PBAT raw material by the lignin can realize the high-value utilization of the lignin and effectively reduce the cost of the PBAT raw material.
At present, lignin is basically directly blended or blended after lignin is modified by introducing the lignin into the PBAT, the method is simple, but the lignin substitution rate in the composite material prepared by blending the lignin and the PBAT is generally lower than 30%, and the problems of phase separation, poor dispersibility, easy agglomeration and the like exist in a PBAT matrix, so that the industrial production of the composite material is difficult to realize. In recent years, methylation modification of lignin and introduction of maleic anhydride have been studied to improve substitution rate to 60% and maintain good mechanical properties. However, the process has higher complexity, and if the mechanical properties of the substitution rate are further improved, the mechanical properties are difficult to ensure.
In view of the above drawbacks, the present invention has been made through research experiments.
Disclosure of Invention
The invention aims to provide a preparation method of polybutylene adipate terephthalate with high lignin content, which is used for overcoming the technical defects.
In order to achieve the above object, the present invention provides a method for preparing polybutylene adipate terephthalate with high lignin content, which comprises the steps of introducing lignin molecules into polybutylene adipate terephthalate molecular chains by melt polycondensation, and subsequently introducing lignin into polybutylene adipate terephthalate containing lignin by melt blending, thereby further increasing lignin content, comprising the following four steps:
(1) In the esterification stage, adding the mixture of adipic acid and 1, 4-butanediol into a polycondensation reaction kettle, stirring, then adding trimethylolethane serving as a chain extender, and heating to perform esterification reaction;
(2) In the transesterification stage, dimethyl terephthalate and 1, 4-butanediol are added in the step (1), tetra-n-butyl titanate is added after stirring, and the temperature is raised for transesterification reaction;
(3) In the melt polycondensation stage, adding lignin, a titanium phosphorus compound, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite into the step (2), heating, melt polycondensing, cooling and granulating to obtain polybutylene adipate terephthalate replaced by lignin;
(4) And in the melt blending stage, premixing the lignin-substituted polybutylene adipate terephthalate and lignin, transferring into a double-screw extruder, heating, melting, blending, cooling, and granulating to obtain the polybutylene adipate terephthalate with high lignin content.
In the step (1) and the step (2), the mole ratio of adipic acid, 1, 4-butanediol and dimethyl terephthalate is 1: (2.7 to 3.0): 1, a step of;
the mass ratio of the 1, 4-butanediol added in the step (1) and the step (2) is 1:1.2-2.0.
The addition amount of the trimethylolethane in the step (1) is 1.0-4.0 per mill of the total amount of the raw materials in the step (1).
In the step (1), the esterification reaction temperature is 150-160 ℃, and the acid value is 1.8-2.2mg KOH/g, so that the reaction end point is reached.
The adding amount of the tetrabutyl titanate in the step (2) is 0.15-0.35 per mill of the total amount of the raw materials in the step (2).
The transesterification reaction temperature in the step (2) is 210-220 ℃ and the reaction time is 2-3h.
The lignin addition amount in the step (3) is 2-6%; the dosage of the titanium phosphorus compound of the catalyst is 0.4 to 0.8 per mill; the dosage of the N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine is 0.05-0.2%; the dosage of the bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is 0.1 to 0.5 per mill.
In the step (3), the melt polycondensation temperature is 220-235 ℃, the reaction pressure is vacuumized to 1kPa, and the reaction time is 2-4 hours.
The mass ratio of lignin-substituted polybutylene adipate terephthalate to lignin in the step (4) is 1: (1.0 to 1.5).
And (3) in the step (4), the processing temperature of melt blending is 125-140 ℃, and the melt blending is carried out by circulating for at least 2 times into a double-screw extruder.
The lignin comprises kraft lignin, alkali lignin, hydrolytic lignin, enzymatic lignin and organic solvent lignin which are obtained from different raw materials through different treatment methods; different raw materials comprise various woody plants, herbaceous plants and vascular plants, and different treatment methods comprise acid, alkali, supercritical, aqueous two-phase, ionic liquid, organic solvent and enzyme.
Compared with the prior art, the invention has the advantages that: according to the invention, lignin is directly added in the synthesis stage, and can be used as a copolymer unit to be introduced into a polybutylene adipate terephthalate chain, so that the stability and the dispersibility are excellent; in addition, lignin molecules in the polymer chain are beneficial to improving the dispersibility and compatibility of lignin added in a blending mode in the later period, and the defect of poor mechanical property of polybutylene adipate terephthalate caused by high-level lignin substitution rate is remarkably improved.
According to the method, the lignin substitution rate is 2-6% in the polycondensation synthesis process, the overall lignin substitution rate after the blending process can exceed 60%, and good mechanical properties are maintained. The lignin with excellent degradation performance can also ensure the excellent degradation performance of the composite material. The preparation process has simple process flow and can realize industrialization.
Detailed Description
The following examples are given in detail for the purpose of better understanding of the technical content of the present invention, and are not intended to limit the scope of the present invention.
Example 1
Esterification stage: adding 1460g of adipic acid and 1170g of 1, 4-butanediol mixture into a polycondensation reaction kettle, stirring, then adding 11.2g of trimethylolethane, heating to 150-160 ℃, reacting for 2 hours, and determining that the acid value is 2mg KOH/g to reach the end of the reaction;
transesterification stage: 1940g of dimethyl terephthalate and 1530g of 1, 4-butanediol are added into the system, 0.8g of tetra-n-butyl titanate is added after stirring, the temperature is raised to 210 ℃, and the reaction is carried out for 2.5 hours, so as to reach the end of the reaction;
melt polycondensation stage: 200g of lignin, 1.9g of titanium phosphate, 0.3g of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 0.9g of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite are added into the system, the temperature is raised to 230 ℃, and the mixture is vacuumized to 1kPa for 3 hours, and then cooled and pelletized to obtain polybutylene adipate terephthalate with lignin substitution rate of about 6%.
Melt blending stage: 3000g of polybutylene adipate terephthalate pellets having a lignin substitution of about 6% and 4500g of lignin were premixed and subsequently transferred to a twin-screw extruder, the processing temperature was set to 130 ℃, cycled 3 times, and cooled and pelletized to yield polybutylene adipate terephthalate having a lignin substitution of about 63%. The tensile strength (MD/TD) of the obtained film was 59MPa/44MPa, and the test method was referred to GB/T1040.3.
Example 2
The procedure and procedure were as in example 1, except that 100g of lignin was added in the melt polycondensation stage, polybutylene adipate terephthalate was obtained having a lignin substitution rate of about 4.2%.
Melt blending stage: 3000g of polybutylene adipate terephthalate pellets having a lignin substitution of about 4.2% and 4500g of lignin were premixed and subsequently transferred to a twin screw extruder, the processing temperature was set to 130 ℃, cycled 3 times, and cooled and pelletized to yield polybutylene adipate terephthalate having a lignin substitution of about 61%. The tensile strength (MD/TD) of the obtained film was 56MPa/44MPa, and the test method was referred to GB/T1040.3.
Example 3
The method and procedure were the same as in example 1, except that lignin was not added in the melt polycondensation stage, but polybutylene adipate terephthalate was obtained in the melt blending stage at a lignin substitution rate of about 33%. The tensile strength (MD/TD) of the obtained film was 39MPa/44MPa, and the test method was referred to GB/T1040.3.
Example 4
The method and procedure are the same as in example 1, only melt blending stage: 3000g of polybutylene adipate terephthalate pellets with a lignin substitution of about 6% and 1000g of lignin were premixed and subsequently transferred to a twin-screw extruder, the processing temperature was set to 130 ℃, cycled 3 times, and cooled and pelletized to yield polybutylene adipate terephthalate with a lignin substitution of about 48%. The tensile strength (MD/TD) of the obtained film was 48MPa/44MPa, and the test method was referred to GB/T1040.3.
Claims (10)
1. The preparation method of the polybutylene adipate-terephthalate with high lignin content is characterized by comprising the following steps:
(1) In the esterification stage, adding the mixture of adipic acid and 1, 4-butanediol into a polycondensation reaction kettle, stirring, then adding trimethylolethane serving as a chain extender, and heating to perform esterification reaction;
(2) In the transesterification stage, dimethyl terephthalate and 1, 4-butanediol are added in the step (1), tetra-n-butyl titanate is added after stirring, and the temperature is raised for transesterification reaction;
(3) In the melt polycondensation stage, adding lignin, titanium phosphate, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite into the step (2), heating, melt polycondensing, cooling and granulating to obtain polybutylene adipate terephthalate replaced by lignin;
(4) And in the melt blending stage, premixing the lignin-substituted polybutylene adipate terephthalate and lignin, transferring into a double-screw extruder, heating, melting, blending, cooling, and granulating to obtain the polybutylene adipate terephthalate with high lignin content.
2. The method for preparing high lignin content polybutylene adipate terephthalate according to claim 1, wherein in step (1) and step (2), the molar ratio of three monomers of adipic acid, 1, 4-butanediol, and dimethyl terephthalate is 1: (2.7 to 3.0): 1, a step of;
the mass ratio of the 1, 4-butanediol added in the step (1) and the step (2) is 1:1.2-2.0.
3. The method for producing polybutylene adipate terephthalate with high lignin content according to claim 1, wherein the amount of trimethylolethane added in step (1) is 1.0-4.0% by weight of the total amount of the raw materials in step (1).
4. The method for preparing polybutylene adipate terephthalate with high lignin content according to claim 1, wherein the esterification reaction temperature in the step (1) is 150-160 ℃, and the acid value is 1.8-2.2mg KOH/g, which is the reaction end point.
5. The method for producing polybutylene adipate terephthalate with high lignin content according to claim 1, wherein the amount of tetra-n-butyl titanate added in the step (2) is 0.15-0.35 per mill of the total amount of the raw materials in the step (2).
6. The method for preparing polybutylene adipate terephthalate with high lignin content according to claim 1, wherein the transesterification reaction temperature in the step (2) is 210-220 ℃ and the reaction time is 2-3 hours.
7. The method for preparing high lignin content polybutylene adipate terephthalate according to claim 1, characterized in that the lignin addition in step (3) is 2-6%;
the dosage of the catalyst titanium phosphate is 0.4 to 0.8 per mill;
the dosage of the N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine is 0.05-0.2%;
the dosage of the bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is 0.1 to 0.5 per mill.
8. The method for producing polybutylene adipate terephthalate with high lignin content according to claim 1, wherein the melt polycondensation temperature in step (3) is 220-235 ℃, the reaction pressure is evacuated to 1kPa, and the reaction time is 2-4 hours.
9. The method for preparing high lignin content polybutylene adipate terephthalate according to claim 1, wherein the mass ratio of lignin substituted polybutylene adipate terephthalate to lignin in step (4) is 1: (1.0 to 1.5).
10. The method for preparing high lignin content polybutylene adipate terephthalate according to claim 1, wherein the processing temperature of melt blending in step (4) is 125-140 ℃, and the high lignin content polybutylene adipate terephthalate is recycled into a twin-screw extruder at least 2 times for melt blending.
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| DE112010003905T5 (en) * | 2009-10-02 | 2012-11-22 | Kao Corp. | Binder resin for toner |
| CN101921387B (en) * | 2010-09-07 | 2012-01-04 | 西南科技大学 | Lignin modified PET (Polyethylene Terephthalate) composite material and preparation method thereof |
| US20150197667A1 (en) * | 2014-01-15 | 2015-07-16 | Ppg Industries Ohio, Inc. | Polyester polymers comprising lignin |
| CN106832801B (en) * | 2016-12-21 | 2019-07-02 | 济宁明升新材料有限公司 | A kind of lignin modification PBAT biodegradable plastic and preparation method thereof |
| SE545476C2 (en) * | 2020-06-02 | 2023-09-26 | Lignin Ind Ab | Composition comprising polyester and modified softwood lignin |
| CN111607202A (en) * | 2020-07-08 | 2020-09-01 | 浙江晟祺实业有限公司 | Methylated lignin PBAT biodegradable plastic and preparation method thereof |
| CN113278265A (en) * | 2021-06-25 | 2021-08-20 | 华东理工大学 | Degradable lignin-based composite agricultural mulching film and preparation method thereof |
| CN114058161B (en) * | 2021-12-14 | 2022-08-23 | 广东九彩新材料有限公司 | Black master batch capable of completely biodegrading plastic |
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