CN114456359B - Tear-resistant and puncture-resistant PBAT copolyester material and preparation method thereof - Google Patents

Tear-resistant and puncture-resistant PBAT copolyester material and preparation method thereof Download PDF

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CN114456359B
CN114456359B CN202210053507.8A CN202210053507A CN114456359B CN 114456359 B CN114456359 B CN 114456359B CN 202210053507 A CN202210053507 A CN 202210053507A CN 114456359 B CN114456359 B CN 114456359B
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esterification
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pbat
puncture
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CN114456359A (en
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李迎春
李枝茂
刘彤
雷海瑜
杨玉婷
郭欣
王文生
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North University of China
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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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 application belongs to the field of high polymer materials, and particularly relates to a tear-resistant and puncture-resistant PBAT copolyester material and a preparation method thereof; the preparation method of the copolyester material comprises the steps of blending adipic acid, 1, 4-butanediol, terephthalic acid, glycerol and tetrabutyl titanate in molar ratio, and sequentially performing three stages of two-step esterification and polycondensation to obtain PBAT-GL-0.6 copolyester; then, continuously adding citric acid and microcrystalline cellulose for third-step esterification to obtain the tear-resistant and puncture-resistant PBAT copolyester material; according to the synthesis method provided by the application, the puncture performance of the PBAT copolyester material added with 1 weight percent of MCC is 111.89% higher than that of the PBAT copolyester material without MCC, and the tear strength is 78.25%. The preparation method of the application can greatly improve the tearing performance and puncture performance of the PBAT copolyester material, and has high market value.

Description

Tear-resistant and puncture-resistant PBAT copolyester material and preparation method thereof
Technical Field
The application belongs to the field of high polymer materials, relates to synthesis and modification of a PBAT biodegradable material, and in particular relates to a tear-resistant and puncture-resistant PBAT copolyester material and a preparation method thereof.
Background
The development of biodegradable polymers and bio-based materials is receiving extensive and profound attention in both academia and industry for better human harmony with nature. Currently, polymers derived from renewable resources such as natural cellulose and polyester-based composites, including polylactic acid (PLA), polycaprolactone (PCL), poly (hydroxyalkanoate) (PHA), polybutylene succinate (PBS) and poly (butylene adipate-co-terephthalate) (PBAT), are the leading advances achieved in this trend. Among them, PBAT and cellulose composites have been considered for use in the fields of bioengineering, drug delivery, wearable devices, and conventional packaging. The current mainstream methods for preparing PBAT and cellulose composite materials are roughly divided into the following four methods: i, directly blending natural cellulose without any treatment with PBAT; II, in order to improve the compatibility of cellulose and PBAT and strengthen the thermodynamic property of the cellulose, the natural cellulose is treated by acid or alkali; III, adding a small molecule or macromolecule compatibilizer to improve the adhesive force of a phase interface and the mechanical property of the composite material; and IV, in order to be applied to the high-end fields such as sensors, the natural cellulose is modified by organic molecules so as to have the functionality.
However, no matter how the cellulose is blended and treated, the improvement in thermodynamic properties and the enhancement in interfacial bonding force are essentially altered due to the constant non-covalent bonds formed between the PBAT and the cellulose. In order to fundamentally increase the thermodynamic properties and interfacial bonding strength, covalent bonds must be formed between PBAT and cellulose to solve this problem.
Disclosure of Invention
The application overcomes the defects of the prior art and provides a tear-resistant and puncture-resistant PBAT copolyester material. The application not only makes cellulose as a filler to strengthen the mechanical property of the matrix, but also makes the cellulose become a chemical crosslinking point to exist. Thus, the level of the mechanical property improvement of the material can be greatly improved; in addition, the covalent bond between the cellulose and the PBAT can be improved, and the heat resistance of the material can be also improved.
In order to solve the technical problems, the application adopts the following technical scheme: a tear-resistant and puncture-resistant PBAT copolyester material is prepared from the following raw materials:
3.5 parts by mol of AA (adipic acid),
10 parts by mole of BDO (1, 4-butanediol),
3.5 molar parts of TPA (terephthalic acid),
glycerol (GL, glycerol) 0.06 molar parts,
citric acid (CA, citric acid) 0.06 molar parts,
tetrabutyl Titanate (tetrabutyl titanate) 0 to 0.06 molar parts and not 0,
microcrystalline cellulose (MCC, microcrystalline cellulose); wherein the addition amount of the microcrystalline cellulose accounts for 0-5 wt% of the total mass of the obtained PBAT copolyester material.
Further, the tear-resistant and puncture-resistant PBAT copolyester material is prepared from the following raw materials:
3.5 parts by mol of AA (adipic acid),
10 parts by mole of BDO (1, 4-butanediol),
3.5 molar parts of TPA (terephthalic acid),
glycerol (GL, glycerol) 0.06 molar parts,
citric acid (CA, citric acid) 0.06 molar parts,
tetrabutyl Titanate (tetrabutyl titanate) 0 to 0.06 molar parts and not 0,
microcrystalline cellulose (MCC, microcrystalline cellulose); wherein the addition amount of the microcrystalline cellulose accounts for 1-5 wt% of the total mass of the obtained PBAT copolyester material.
In addition, the application also provides a preparation method of the tear-resistant and puncture-resistant PBAT copolyester material, which comprises the steps of blending adipic acid, 1.4-butanediol, terephthalic acid, glycerol and tetrabutyl titanate in a molar ratio, and sequentially performing three stages of two-step esterification and polycondensation to obtain the PBAT-GL-0.6 copolyester; then, continuously adding citric acid and microcrystalline cellulose for the third esterification, and obtaining the tear-resistant and puncture-resistant PBAT copolyester material.
Through the above synthetic steps, firstly, esterification reaction is carried out between the crosslinking agent CA and secondary hydroxyl which is not fully reacted on the monomer GL and active hydroxyl on MCC, so that stable chemical crosslinking is formed between MCC and PBAT, and interface combination is more perfect; in addition, cellulose has a physical reinforcing effect on the PBAT polyester matrix as a filler. By combining the two points, the tearing performance and the puncture performance of the material are greatly improved by chemical crosslinking, interfacial binding force improvement and physical enhancement.
Further, the first stage esterification temperature, the second stage esterification temperature, the polycondensation temperature and the third stage esterification temperature are respectively: 120-170 ℃, 200-230 ℃, 220-255 ℃ and 140-180 ℃.
Further, the pressure of the first stage esterification, the pressure of the second stage esterification, the pressure of the polycondensation, and the pressure of the third stage esterification are respectively: 0.1-0.15 MPa, 220-700 Pa and 500-1000 Pa.
Compared with the prior art, the application has the following beneficial effects:
according to the synthesis method provided by the application, the puncture performance of the PBAT copolyester material added with 1wt% of MCC is 111.89% higher than that of the PBAT copolyester material without MCC; the tear strength of the PBAT copolyester material with 1wt% MCC added was 78.25% improved over that of the PBAT copolyester material without MCC added. The preparation method of the application can greatly improve the tearing performance and puncture performance of the PBAT copolyester material, and has high market value.
Drawings
FIG. 1 is a graph showing the results of infrared detection experiments on copolyester materials according to the control sample and the examples of the present application.
Detailed Description
The application is further illustrated below with reference to specific examples.
Example 1
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 7g of MCC are added, the vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on the equipment is not changed, the experiment is ended, and the result is marked as MCP-0.5.
Example 2
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 14g of MCC are added, the vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on the equipment is not changed, the experiment is ended, and the MCP-1 is marked.
Example 3
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, a nitrogen valve and a deflation valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 28g of MCC are added, a vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on equipment is not changed, the experiment is ended, and the result is marked as MCP-2.
Example 4
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is increased to 200-230 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 42g of MCC are added, the vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on the equipment is not changed, the experiment is ended, and the MCP-3 is marked.
Example 5
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 56g of MCC are added, the vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on the equipment is not changed, the experiment is ended, and the result is marked as MCP-4.
Example 6
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation and a third-stage esterification method, and are blended at the temperature of 140 ℃ without adding a catalyst, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); beginning the polycondensation stage, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) and heating to 240 ℃, wherein the pressure is 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of CA and 70g of MCC are added, the vacuum pump is opened, the third stage of esterification is started, after 50 minutes of reaction, when the torque on the equipment is not changed, the experiment is finished, and the MCP-5 is marked.
Control group 1
511.49g of AA (adipic acid), 900g of BDO (1.4-butanediol), 581g of TPA (terephthalic acid) and 5.52g of GL (glycerol) are weighed by a two-stage esterification and one-stage polycondensation method, and are blended under the condition of no catalyst and at the temperature of 140 ℃, and then the first-stage esterification is started, wherein the pressure is 0.12MPa, and the esterification is carried out for 1.3 hours; starting the second stage of esterification, adding a catalyst Tetrabutyl Titanate (tetrabutyl titanate) to perform esterification when the temperature is raised to 210 ℃, and reacting for about 3.5 hours, wherein when the mass of the produced water is equivalent to that of theoretical water (90-110 percent); the polycondensation stage was started, catalyst Tetrabutyl Titanate (tetrabutyl titanate) was added and heated to 240℃under 500Pa, after 5.5h polycondensation, and when no change in torque on the equipment was found, the experiment was ended and designated as P-0.
Detection result:
the tear strength and puncture strength of a high tear, high puncture PBAT copolyester material prepared in control group 1, example 2, example 3, example 4, example 5 and example 6 were measured, respectively. Wherein, the test method of tearing strength in GB/T529-2008 vulcanized rubber or thermoplastic rubber (trouser, right angle and crescent test sample) is adopted, the length of the test sample is 100mm, the width is 16mm, and the incision length is 40mm; the calculation formula is T S =f/d, where T S (N/mm) is the tear strength, F (N) is the force required to tear the specimen, and d (mm) is the median of the specimen thickness. The test sample is formed by hot pressing and then cold pressing by a flat vulcanizing machine, and is cut, and the test temperature is 25 ℃. Taking the puncture resistance strength of the sample as the median of 5 data of three experiments, and the test results are shown in table 1; the puncture strength test method in GB/T10004-2008 composite plastic film for packaging, bag dry method composite and extrusion composite is adopted, the diameter of a test sample is 30mm, and the average thickness is 0.50+/-0.05 mm. The test sample is a plate sheet which is formed by hot pressing and cold pressing by a plate vulcanizing machine, is cut into a specification of 30mm in diameter, and has a test temperature of 25 ℃. The puncture resistance of the sample was averaged over 5 data from three experiments, and the test results are shown in table 2.
As can be seen from table 1, from the control group and examples 1 to 6, it can be derived that: the tear strength of the tear-resistant and puncture-resistant PBAT copolyester material provided by the application is increased along with the increase of the MCC in parts by mass, and then the tear strength of the PBAT copolyester material is decreased. The tear strength of the PBAT copolyester material was 109.26N/mm without the addition of MCC. With the addition of only 0.5% wt, the tear strength of the PBAT copolyester material was 142.48N/mm. With the addition of only 1% wt, the tear strength of the PBAT copolyester material was 194.76N/mm. With the addition of only 2% wt, the tear strength of the PBAT copolyester material was 173.28N/mm. With the addition of only 3% wt, the tear strength of the PBAT copolyester material was 154.26N/mm. With the addition of only 4% wt, the tear strength of the PBAT copolyester material was 138.48N/mm. With the addition of only 5% wt, the tear strength of the PBAT copolyester material was 136.96N/mm.
Table 1: tear strength detection result of tear-resistant and puncture-resistant PBAT copolyester material embodiment
As can be seen from table 2, from the control group and examples 1 to 6, it can be derived that: the puncture strength of the high-tearing and high-puncture PBAT copolyester material provided by the application is increased along with the increase of the MCC in parts by mass, and then the puncture strength of the PBAT copolyester material is decreased. The puncture strength of the PBAT copolyester material was 12.02N without the addition of MCC. With the addition of only 0.5% wt, the puncture strength of the PBAT copolyester material was 23.15N. With the addition of only 1% wt, the puncture strength of the PBAT copolyester material was 25.47N. With the addition of only 2% wt, the puncture strength of the PBAT copolyester material was 19.75N. With the addition of only 3% wt, the puncture strength of the PBAT copolyester material was 17.84N/mm. With the addition of only 4% wt, the puncture strength of the PBAT copolyester material was 15.27N. With the addition of only 5% wt, the puncture strength of the PBAT copolyester material was 15.16N.
Table 2: puncture strength detection result of tear-resistant and puncture-resistant PBAT copolyester material embodiment
As can be seen from FIG. 1, citric acid was found at 1754, 1745 and 1711cm -1 The stretching peak with c=o at the spot does not appear in the sample examinedThis suggests that citric acid is involved in the reaction in the system, and that PBAT and MCC are not blended together from the side.
Experimental results show that the penetration performance of the PBAT copolyester material added with 1 weight percent of MCC is 111.89 percent higher than that of the PBAT copolyester material without MCC; the tear strength of the PBAT copolyester material added with 1 weight percent of MCC is increased by 78.25 percent compared with that of the PBAT copolyester material without the MCC. The preparation method of the application can greatly improve the tearing performance and puncture performance of the PBAT copolyester material, and has high market value.

Claims (1)

1. A preparation method of a tear-resistant and puncture-resistant PBAT copolyester material is characterized in that 511.49g of adipic acid, 900g of 1.4-butanediol, 581g of terephthalic acid and 5.52g of glycerol are weighed by a two-stage esterification, one-stage polycondensation and a third-stage esterification method, blending is carried out under the condition of no catalyst and at the temperature of 140 ℃, the first-stage esterification is started immediately, the pressure is 0.12MPa, and after esterification for 1.3 hours; starting the second stage of esterification, adding a catalyst tetrabutyl titanate for esterification when the temperature is increased to 210 ℃, and reacting for 3.5 hours, wherein the mass of the produced water is 90-110% of that of theoretical water; starting the polycondensation stage, adding tetrabutyl titanate as a catalyst, heating to 240 ℃, keeping the pressure at 500Pa, and after polycondensation for 3 hours, when the torque on the equipment reaches 2.0, turning off heating; when the temperature is reduced to 200 ℃, the polycondensation stage is closed, the nitrogen valve and the air release valve are opened, when the temperature is reduced to 160 ℃ by utilizing nitrogen, the nitrogen valve is closed, 11.52g of citric acid and 14g of microcrystalline cellulose are added, a vacuum pump is opened, the third-stage esterification is started, and after 50 minutes of reaction, the tear-resistant and puncture-resistant PBAT copolyester material is obtained when the torque on equipment is not changed.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112063141A (en) * 2020-08-14 2020-12-11 安徽丰原生物新材料有限公司 Cellulose polyester composite material and preparation method thereof
CN112280014A (en) * 2020-11-06 2021-01-29 中北大学 Puncture-resistant PBSeT biodegradable material and preparation method thereof
CN113185815A (en) * 2021-05-17 2021-07-30 中北大学 Biodegradable material for improving PBSeT puncture resistance by using vinegar residue and preparation method thereof
CN113683757A (en) * 2021-09-01 2021-11-23 中北大学 Tear-resistant environment-friendly PBSeT copolyester material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112063141A (en) * 2020-08-14 2020-12-11 安徽丰原生物新材料有限公司 Cellulose polyester composite material and preparation method thereof
CN112280014A (en) * 2020-11-06 2021-01-29 中北大学 Puncture-resistant PBSeT biodegradable material and preparation method thereof
CN113185815A (en) * 2021-05-17 2021-07-30 中北大学 Biodegradable material for improving PBSeT puncture resistance by using vinegar residue and preparation method thereof
CN113683757A (en) * 2021-09-01 2021-11-23 中北大学 Tear-resistant environment-friendly PBSeT copolyester material and preparation method thereof

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