CN113512187A - Transparent and degradable PBAT material, preparation method and application thereof - Google Patents
Transparent and degradable PBAT material, preparation method and application thereof Download PDFInfo
- Publication number
- CN113512187A CN113512187A CN202110816474.3A CN202110816474A CN113512187A CN 113512187 A CN113512187 A CN 113512187A CN 202110816474 A CN202110816474 A CN 202110816474A CN 113512187 A CN113512187 A CN 113512187A
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- pbat
- pbat material
- preparation
- molar ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G63/66—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention provides a transparent and degradable PBAT material, wherein a prepolymer A formed by bio-based dihydric alcohol and aromatic dibasic acid is added in the preparation process, and the weight percentage of the prepolymer A in the PBAT material is 5-15%. The invention also provides a preparation method of the PBAT material and application of the PBAT material in preparation of a membrane product. The PBAT material provided by the invention has high transparency through modification, is obviously superior to common commercially available membrane-grade PBAT materials, also retains excellent degradability, has a wider application range compared with the existing PBAT materials, is especially suitable for membrane products, and has a very good application prospect. The preparation method of the PBAT material provided by the invention is simple and convenient, does not need high cost, and can be suitable for large-scale and industrial production.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to a transparent and degradable PBAT material, a preparation method thereof and application thereof in preparing a film product.
Background
Polybutylene adipate-co-terephthalate (PBAT) is a biodegradable plastic which is polymerized by using Adipic Acid (AA), terephthalic acid (PTA) and Butanediol (BDO) as monomers. Like other aliphatic polyesters and aromatic polyesters, PBAT has good degradability, excellent mechanical properties and good ductility, and can be applied to the fields of food packaging films, agricultural films, disposable plastic bags, disposable plastic tableware and the like.
So far, PBAT in all commercial degradable materials in the market has the widest application range and the lowest cost, but products such as disposable lunch boxes, plastic bags and the like prepared by PBAT are all milky and opaque, and the application of the PBAT in certain scenes needing transparency is seriously influenced. At present, the development of transparent degradable materials is urgently needed.
Therefore, the development of a PBAT material with good transparency and degradability is urgently needed to further expand the application range thereof.
Disclosure of Invention
To remedy the deficiencies of the prior art, it is an object of the present invention to provide a transparent and degradable PBAT material which is significantly improved in transparency by modification and which also has good degradability.
It is another object of the invention to provide a method for the preparation of said PBAT material.
It is also an object of the invention to provide a use of said PBAT material.
The transparent and degradable PBAT material is added with a prepolymer A formed by bio-based dihydric alcohol and aromatic dibasic acid in the preparation process, wherein the bio-based dihydric alcohol is one or two of isosorbide and isohexide, the aromatic dibasic acid is one or more of terephthalic acid, phthalic acid and 1, 4-naphthalene dicarboxylic acid, and the weight percentage of the prepolymer A in the PBAT material is 5-15%.
In some preferred embodiments, the weight percentage of the prepolymer a in the PBAT material is 5 to 10%.
In some preferred embodiments, the bio-based diol is a mixture of isosorbide and isohexide. In some more preferred embodiments, the bio-based diol is a mixture of isosorbide and isohexide in a molar ratio of 1-2: 1.
In some preferred embodiments, the aromatic diacid is a mixture of terephthalic acid and phthalic acid. In some more preferred embodiments, the aromatic dibasic acid is a mixture of terephthalic acid and phthalic acid in a molar ratio of 1-2: 1.
In some preferred embodiments, the prepolymer a is prepared by a process comprising: mixing the bio-based diol and the aromatic dibasic acid according to the molar ratio of hydroxyl to carboxyl of 1-1.5: 1, and polymerizing to form the prepolymer A under the action of a titanium catalyst or an antimony catalyst.
In some more preferred embodiments, the antimony-based catalyst is one or a mixture of antimony trioxide and antimony acetate. The titanium catalyst is a heterogeneous titanium catalyst which takes isopropyl titanate as a base material and is organically modified.
In some more preferred embodiments, the titanium-based catalyst or the antimony-based catalyst is used in an amount of 1 to 3 wt% based on the total weight of the bio-based glycol and the aromatic dibasic acid.
In some further preferred embodiments, during the preparation of the prepolymer a, the polymerization reaction is performed at a reaction temperature of 230 to 260 ℃, preferably 230 to 240 ℃, and a reaction pressure of 0.05 to 0.2 MPa, preferably 0.1 to 0.15 MPa, and the polymerization reaction is performed under a nitrogen atmosphere.
In some preferred embodiments, the prepolymer A has a number average molecular weight of 3000 to 6000 g/mol and a viscosity of 0.21 to 0.42 dL/g.
In some preferred embodiments, the PBAT material has a number average molecular weight of 180000 to 300000 g/mol and a viscosity of 0.75 to 0.85 dL/g. In some more preferred embodiments, the PBAT material has a number average molecular weight of 180000 to 200000 g/mol and a viscosity of 0.75 to 0.80 dL/g.
The invention also provides a preparation method of the transparent and degradable PBAT material, which is prepared by copolymerizing the prepolymer A, the prepolymer B and the prepolymer C in the presence of a chain extender; the prepolymer B is formed by butanediol and terephthalic acid, and the prepolymer C is formed by butanediol and adipic acid.
In some preferred embodiments, the weight ratio of the prepolymer A, the prepolymer B and the prepolymer C is 0.5-1.5: 3-6. In some more preferred embodiments, the weight ratio of prepolymer a, prepolymer B, prepolymer C is 0.5-1.5: 4-5.5, including but not limited to the weight ratio of prepolymer a, prepolymer B, prepolymer C is 1:5:4, 1.5: 4.5:4, 0.5: 5.5: 4, 1.5: 4: 4.5, etc.
In some preferred embodiments, the prepolymer C accounts for less than 50% of the total weight of the prepolymer a, the prepolymer B and the prepolymer C, and the amount of the prepolymer C is controlled to ensure the degradability of the prepared PBAT material.
In some preferred embodiments, the reaction temperature of the copolymerization reaction of the prepolymer A, the prepolymer B and the prepolymer C is 250 to 280 ℃, the vacuum pressure is 50 to 100 Pa, and the stirring speed is 50 to 100 rpm.
In some preferred embodiments, the prepolymer B is formed by butanediol and terephthalic acid according to a molar ratio of 1.1-1.2: 1, and has a number average molecular weight of 2000-5000 g/mol and a viscosity of 0.15-0.40 dL/g. In some more preferred embodiments, the prepolymer B is prepared by a process comprising: and mixing the butanediol and the terephthalic acid, and polymerizing to form the prepolymer B under the action of a titanium catalyst or an antimony catalyst. The titanium catalyst or the antimony catalyst can be the same as the catalyst used in the preparation of the prepolymer A, and the dosage of the titanium catalyst or the antimony catalyst is 1-3 wt% of the total weight of the butanediol and the terephthalic acid.
In some further preferred embodiments, during the preparation of the prepolymer B, the polymerization reaction is performed at a reaction temperature of 240 to 250 ℃ and a reaction pressure of 0.1 to 0.15 MPa, and the polymerization reaction is performed in a nitrogen atmosphere.
In some preferred embodiments, the prepolymer C is a prepolymer formed by butanediol and adipic acid according to a molar ratio of 1.1-1.2: 1, and has a number average molecular weight of 4000-8000 g/mol and a viscosity of 0.28-0.45 dL/g. In some more preferred embodiments, the prepolymer C is prepared by a process comprising: and mixing the butanediol and the adipic acid, and polymerizing to form the prepolymer C under the action of a titanium catalyst or an antimony catalyst. The titanium catalyst or the antimony catalyst can be the same as the catalyst used in the preparation of the prepolymer A, and the dosage of the titanium catalyst or the antimony catalyst is 1-3 wt% of the total weight of the butanediol and the adipic acid.
In some further preferred embodiments, during the preparation of the prepolymer C, the polymerization reaction is performed at a reaction temperature of 240 to 250 ℃ and a reaction pressure of 0.1 to 0.15 MPa, and the polymerization reaction is performed in a nitrogen atmosphere.
In some preferred embodiments, the chain extender is one or more of the chain extender Joncryl ADR-4368, the chain extender SAG-005, the chain extender SAG-008, 1, 5-naphthalene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2-bis (2-oxazoline), hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, maleic anhydride, pyromellitic anhydride, 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline), isohexide-2, 5-bis (2-oxazoline), the dosage of the prepolymer is 0.5-5 wt% of the total weight of the prepolymer A, the prepolymer B and the prepolymer C.
The invention also provides the use of the transparent and degradable PBAT material according to any of the above technical schemes in the preparation of film products.
The PBAT material provided by the invention has high transparency through modification, is obviously superior to common commercially available membrane-grade PBAT materials, also retains excellent degradability, has a wider application range compared with the existing PBAT materials, is especially suitable for membrane products, and has a very good application prospect. The preparation method of the PBAT material provided by the invention is simple and convenient, does not need high cost, and can be suitable for large-scale and industrial production.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The raw materials or reagents used in the examples of the present invention are all commercially available products unless otherwise specified; the test methods (including number average molecular weight, viscosity, etc.) used in the examples of the present invention are all the conventional test methods in the art unless otherwise specified.
The percentages used in the examples of the present invention are all percentages by mass, unless otherwise specified.
Example 1 preparation of highly transparent, degradable PBAT
The preparation steps are as follows:
1. isosorbide and isohexide (model 1328E) with the molecular weight of 200 and the functionality of 2 are mixed into a diol mixture according to the molar ratio of 2:1, then the diol mixture is mixed with a 1:1 molar ratio mixture of terephthalic acid and phthalic acid according to the molar ratio of hydroxyl to carboxyl of 1.1:1, antimony trioxide catalyst with the total mass of 1 ‰ of reactants is added, the mixture is rapidly stirred under the conditions of 230-.
2. Mixing butanediol and terephthalic acid according to a molar ratio of 1.15:1, adding an antimony trioxide catalyst with the total mass of 1 per thousand of reactants, pressurizing and rapidly stirring at 0.1-0.15 Mpa at the temperature of 240-.
3. Mixing butanediol and adipic acid according to a molar ratio of 1.1:1, adding an antimony trioxide catalyst with the total mass of the reactants being 1 per thousand, pressurizing and rapidly stirring at 0.1-0.15 Mpa at the temperature of 240-.
4. Mixing the three prepolymers according to the weight ratio of 1:5:4, adding a compound mixture of a chain extender SAG-005 and a chain extender SAG-008 according to the mass ratio of 1:1, wherein the addition amount is 3 per mill of the total weight of the three prepolymers, vacuumizing to 50 pa at 260-270 ℃, stirring at 60 rpm, and reacting for 4 hours to obtain the final terpolymer modified high-transparency degradable PBAT material, wherein the number average molecular weight is 200000 g/mol, and the viscosity is 0.78 dL/g.
The resulting material was heated to 200 ℃ under 3000 kg pressure, vacuum-pressed to 50 μm film, and PETG film of the same thickness, ordinary commercial film grade PBAT of the same thickness, were subjected to transmittance test under ASTM D1003 standard conditions, refractive index test under ASTM D542 standard conditions, and gloss test under ASTM E308 standard conditions. The results are shown in Table 1.
TABLE 1
| Material | Thickness (μm) | Transmittance (%) | Refractive index (%) | Degree of gloss |
| PETG film | 50 | 90.1 | 1.57 | 159 |
| Example 1 film | 50 | 91.2 | 1.56 | 162 |
| Ordinary PBAT film | 50 | 49.1 | 1.21 | 36 |
The results in table 1 show that the film prepared from the PBAT material prepared in example 1 of the present invention has a higher transmittance, a refractive index and a gloss that are also as good as those of the PETG film of the same thickness, and even better, and is significantly better than the conventional PBAT film.
Example 2 preparation of highly transparent, degradable PBAT
The preparation steps are as follows:
1. isosorbide and isohexide (same as example 1) are mixed into a dihydric alcohol mixture according to the molar ratio of 1.5:1, then the dihydric alcohol mixture is mixed with a mixture of terephthalic acid and phthalic acid according to the molar ratio of hydroxyl to carboxyl of 1.1:1, antimony acetate catalyst with the total mass of 1 per thousand of the reactants is added, the mixture is rapidly stirred under the conditions of 230-240 ℃ and nitrogen and the pressure of 0.1 MPa for reaction for 3 hours, the sampling test is carried out to achieve the number average molecular weight of about 6000 g/mol and the viscosity of about 0.42 dL/g, and the mixture is sealed and stored for later use.
2. Mixing butanediol and terephthalic acid according to a molar ratio of 1.17:1, adding an antimony acetate catalyst with the total mass of reactants being 1 per thousand, pressurizing to 0.1-0.15 Mpa and stirring rapidly at the temperature of 240-250 ℃ in a nitrogen environment, reacting for 3-3.5 h, sampling and testing to obtain the product with the number average molecular weight of about 5000 g/mol and the viscosity of about 0.40 dL/g, and sealing and storing for later use.
3. Mixing butanediol and adipic acid according to a molar ratio of 1.1:1, adding an antimony acetate catalyst with the total mass of reactants being 1 per thousand, pressurizing and rapidly stirring at 0.1-0.15 Mpa at the temperature of 240-250 ℃ and in a nitrogen environment, reacting for 3 h, sampling and testing to obtain a number average molecular weight of about 8000 g/mol and a viscosity of about 0.45 dL/g, and sealing and storing for later use.
4. Mixing the three prepolymers according to the weight ratio of 1:4.5:4.5, adding a compound mixture of a chain extender SAG-005 and a chain extender SAG-008 according to the mass ratio of 1.5:1, wherein the addition amount is 4 per mill of the total weight of the three prepolymers, vacuumizing to 50 pa at 260 ℃ and 270 ℃, stirring at 60 rpm, and reacting for 4 hours to obtain the final ternary polymerization modified high-transparency degradable PBAT material, wherein the number average molecular weight is 185000 g/mol, and the viscosity is 0.78 dL/g.
The resulting material was heated to 200 ℃ under 3000 kg pressure, vacuum-pressed to 50 μm film, and PETG film of the same thickness, ordinary commercial film grade PBAT of the same thickness, were subjected to transmittance test under ASTM D1003 standard conditions, refractive index test under ASTM D542 standard conditions, and gloss test under ASTM E308 standard conditions. The results are shown in Table 2.
TABLE 2
| Material | Thickness (μm) | Transmittance (%) | Refractive index (%) | Degree of gloss |
| PETG film | 50 | 90.1 | 1.57 | 159 |
| Example 2 film | 50 | 92.2 | 1.59 | 160 |
| Ordinary PBAT film | 50 | 49.1 | 1.21 | 36 |
The results in table 2 show that the film prepared from the PBAT material prepared in example 2 of the present invention has a higher transmittance, a refractive index and a gloss that are also as good as those of the PETG film of the same thickness, and even better, and is significantly better than the conventional PBAT film.
Example 3 preparation of highly transparent, degradable PBAT
The preparation steps are as follows:
1. isosorbide and isohexide (same as example 1) are mixed into a diol mixture according to the molar ratio of 1.2:1, then the diol mixture is mixed with a 1.5:1 molar ratio mixture of terephthalic acid and phthalic acid according to the molar ratio of hydroxyl to carboxyl of 1.1:1, antimony trioxide catalyst with 1 ‰ of the total mass of reactants is added, the reaction is carried out for 3 hours under the conditions of 230-.
2. Mixing butanediol and terephthalic acid according to a molar ratio of 1.2:1, adding an antimony trioxide catalyst with the total mass of 1 per thousand of reactants, pressurizing and rapidly stirring at 0.1-0.15 Mpa at the temperature of 240-.
3. Mixing butanediol and adipic acid according to a molar ratio of 1.2:1, adding an antimony trioxide catalyst with the total mass of the reactants being 1 per thousand, pressurizing and rapidly stirring at 0.1-0.15 Mpa at the temperature of 240-.
4. Mixing the three prepolymers according to a weight ratio of 0.5:5:4.5, adding a compound mixture of a chain extender SAG-005 and a chain extender SAG-008 according to a mass ratio of 3:1, wherein the addition amount is 3 per mill of the total weight of the three prepolymers, vacuumizing to 50 pa at 260-270 ℃, stirring at 60 rpm, and reacting for 4 hours to obtain the final ternary polymerization modified high-transparency degradable PBAT material, wherein the number average molecular weight is 190000 g/mol, and the viscosity is 0.80 dL/g.
The resulting material was heated to 200 ℃ under 3000 kg pressure and vacuum pressed to 50 μm film sheets and PETG film of the same thickness, ordinary commercial film grade PBAT of the same thickness, transmission tested under ASTM D1003, refractive index tested under ASTM D542, and gloss tested under ASTM E308. The results are shown in Table 3.
TABLE 3
| Material | Thickness (μm) | Transmittance (%) | Refractive index (%) | Degree of gloss |
| PETG film | 50 | 90.1 | 1.57 | 159 |
| Example 3 film | 50 | 90.5 | 1.57 | 163 |
| Ordinary PBAT film | 50 | 49.1 | 1.21 | 36 |
The results in table 3 show that the film prepared from the PBAT material prepared in example 3 of the present invention has a higher transmittance, a refractive index and a gloss that are also as good as those of the PETG film of the same thickness, and even better, and is significantly better than the conventional PBAT film.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (10)
1. The transparent and degradable PBAT material is characterized in that a prepolymer A formed by bio-based diol and aromatic diacid is added in the preparation process of the PBAT material, wherein the bio-based diol is one or two of isosorbide and isohexide, the aromatic diacid is one or more of terephthalic acid, phthalic acid and 1, 4-naphthalene dicarboxylic acid, and the weight percentage of the prepolymer A in the PBAT material is 5-15%.
2. The PBAT material of claim 1, wherein the bio-based diol is a mixture of isosorbide and isohexide in a molar ratio of 1-2: 1; and/or
The aromatic dibasic acid is a mixture formed by terephthalic acid and phthalic acid according to a molar ratio of 1-2: 1.
3. The PBAT material of claim 1 or 2, characterized in that the preparation of the prepolymer a comprises: mixing the bio-based diol and the aromatic dibasic acid according to the molar ratio of hydroxyl to carboxyl of 1-1.5: 1, and polymerizing under the action of a titanium catalyst or an antimony catalyst to form the prepolymer A; preferably, the antimony catalyst is one or two of antimony trioxide and antimony acetate; the dosage of the titanium catalyst or the antimony catalyst is 1-3 wt% of the total weight of the bio-based diol and the aromatic dibasic acid.
4. The PBAT material of any of claims 1 to 3, wherein the prepolymer A has a number average molecular weight of 3000 to 6000 g/mol and a viscosity of 0.21 to 0.42 dL/g.
5. The PBAT material of any of claims 1-4, characterized in that the PBAT material has a number average molecular weight of 180000-300000 g/mol and a viscosity of 0.75-0.85 dL/g.
6. The method for preparing a transparent and degradable PBAT material according to any of claims 1 to 5, characterized in that the PBAT material is prepared by copolymerizing prepolymer a with prepolymer B, prepolymer C in the presence of a chain extender; the prepolymer B is formed by butanediol and terephthalic acid, and the prepolymer C is formed by butanediol and adipic acid.
7. The preparation method according to claim 6, wherein the weight ratio of the prepolymer A, the prepolymer B and the prepolymer C is 0.5-1.5: 3-6, preferably 0.5-1.5: 4-5.5, and the prepolymer C accounts for less than 50 wt.% of the total weight of the prepolymer A, the prepolymer B and the prepolymer C.
8. The preparation method according to claim 6 or 7, wherein the prepolymer B is formed by butanediol and terephthalic acid according to a molar ratio of 1.1-1.2: 1, and has a number average molecular weight of 2000-5000 g/mol and a viscosity of 0.15-0.40 dL/g; and/or
The prepolymer C is formed by butanediol and adipic acid according to a molar ratio of 1.1-1.2: 1, the number average molecular weight of the prepolymer C is 4000-8000 g/mol, and the viscosity of the prepolymer C is 0.28-0.45 dL/g.
9. The production method according to claim 7 or 8, wherein the chain extender is one or more of a chain extender Joncryl ADR-4368, a chain extender SAG-005, a chain extender SAG-008, 1, 5-naphthalene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2-bis (2-oxazoline), hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, maleic anhydride, pyromellitic anhydride, 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline), isohexide-2, 5-bis (2-oxazoline), the dosage of the prepolymer is 0.5-5 wt% of the total weight of the prepolymer A, the prepolymer B and the prepolymer C.
10. Use of the transparent and degradable PBAT material according to any of claims 1-5 for the preparation of a film product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110816474.3A CN113512187A (en) | 2021-07-20 | 2021-07-20 | Transparent and degradable PBAT material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110816474.3A CN113512187A (en) | 2021-07-20 | 2021-07-20 | Transparent and degradable PBAT material, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113512187A true CN113512187A (en) | 2021-10-19 |
Family
ID=78067392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110816474.3A Pending CN113512187A (en) | 2021-07-20 | 2021-07-20 | Transparent and degradable PBAT material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113512187A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292387A (en) * | 2021-12-29 | 2022-04-08 | 江苏扬农化工集团有限公司 | Ultraviolet-resistant PBAT-based composite material, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711302A (en) * | 2002-11-13 | 2005-12-21 | 伊斯曼化学公司 | Method for making isosorbide containing polyesters |
| WO2011031112A2 (en) * | 2009-09-14 | 2011-03-17 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
| CN106574041A (en) * | 2014-08-21 | 2017-04-19 | 乐天精密化学株式会社 | Transparent biodegradable polymer |
| CN112048058A (en) * | 2020-08-12 | 2020-12-08 | 东华大学 | Preparation method of high-melting-point crystalline biodegradable copolyester |
-
2021
- 2021-07-20 CN CN202110816474.3A patent/CN113512187A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711302A (en) * | 2002-11-13 | 2005-12-21 | 伊斯曼化学公司 | Method for making isosorbide containing polyesters |
| WO2011031112A2 (en) * | 2009-09-14 | 2011-03-17 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
| CN106574041A (en) * | 2014-08-21 | 2017-04-19 | 乐天精密化学株式会社 | Transparent biodegradable polymer |
| CN112048058A (en) * | 2020-08-12 | 2020-12-08 | 东华大学 | Preparation method of high-melting-point crystalline biodegradable copolyester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292387A (en) * | 2021-12-29 | 2022-04-08 | 江苏扬农化工集团有限公司 | Ultraviolet-resistant PBAT-based composite material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3445801B1 (en) | New polyester and compositions containing it | |
| TWI502020B (en) | Polyester resin and method for preparing the same | |
| EP3119831B1 (en) | Polyesters comprising 2,5-furandicarboxylate and saturated diol units having a high glass transition temperature | |
| JP5223347B2 (en) | Resin composition, method for producing the same, and copolymer | |
| CN113512187A (en) | Transparent and degradable PBAT material, preparation method and application thereof | |
| US5652325A (en) | Production of aliphatic copolyesters | |
| CN115651175B (en) | Antibacterial heat-resistant high-barrier copolyester containing furan ring and preparation method thereof | |
| US20230257520A1 (en) | Process for preparing poly(trimethylene furandicarboxylate) using zinc catalyst | |
| CN115322350A (en) | Degradable bio-based polyester and preparation method and application thereof | |
| JP3374530B2 (en) | Method for producing aliphatic polyester copolymer | |
| CN113493598B (en) | Biodegradable polyester and preparation method thereof | |
| KR102589190B1 (en) | Biodegradable polyester copolymer comprising crosslinked anhydrosugar alcohol-alkylene glycol with isocyanate and preparation method thereof, and molded article comprising the same | |
| CN113501944A (en) | High-barrier and degradable PBAT material, preparation method and application thereof | |
| TW202336081A (en) | thermoplastic copolyester | |
| CN117510810A (en) | PBAT-ETL copolyester material with high elongation at break and preparation method thereof | |
| CN114763406A (en) | Novel copolyesters and their use | |
| EP4039724A1 (en) | Polyester resin including diester compound and anhydrosugar alcohol, and method for preparing same | |
| JP2023074138A (en) | Modified copolyester resin, aqueous dispersion and adhesive composition | |
| CN116262832A (en) | Preparation method of biodegradable block branched copolyester | |
| TW202337950A (en) | Polyester and molded article | |
| JP2015030852A (en) | Method for manufacturing copolyester | |
| CN117681525A (en) | High-barrier bio-based PLA composite film with ultraviolet shielding property and preparation method thereof | |
| CN113831521A (en) | Polyether modified PBAT degradable plastic and preparation method thereof | |
| CN115651174A (en) | Method for synthesizing biodegradable PBAT-PLA copolyester by organic guanidine catalysis | |
| KR20000019018A (en) | Polyester resin composition and process for production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |