阅读说明：本技术 一种高阻隔且可降解的pbat材料及其制备方法、用途 (High-barrier and degradable PBAT material, preparation method and application thereof ) 是由 袁永浩 闫银凤 李丽丽 聂夕冉 周宏涛 黄晓谨 于 2021-07-20 设计创作，主要内容包括：本发明提供了一种高阻隔且可降解的PBAT材料,在制备过程中添加有生物基二元酸和丁二醇所形成的预聚物A,其中,预聚物A在所述PBAT材料中的重量百分比为5～15%。本发明还提供了所述PBAT材料的制备方法以及在制备膜制品中的用途。本发明提供的PBAT材料通过改性可具有较好的阻隔性能,明显优于普通的市售膜级PBAT材料,而且还保留了优异的可降解性,相对于现有的PBAT材料,应用范围更广泛,尤其适用于膜制品,非常具有应用前景。本发明提供的PBAT材料制备方法简便,无需高昂成本,能够适应大规模、工业化生产。(The invention provides a high-barrier and degradable PBAT material, wherein a prepolymer A formed by bio-based dibasic acid and butanediol 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 better barrier property through modification, is obviously superior to common commercially available membrane-grade PBAT materials, also retains excellent degradability, has wider application range compared with the existing PBAT materials, is especially suitable for membrane products, and has 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.)

1. The high-barrier and degradable PBAT material is characterized in that a prepolymer A formed by bio-based dibasic acid and butanediol is added in the preparation process of the PBAT material, wherein the bio-based dibasic acid is one or more of 2, 5-furandicarboxylic acid, succinic acid and 1, 9-azelaic 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 molar ratio of the bio-based diacid to the butanediol is 1:1 to 1.5, preferably 1:1 to 1.2; the bio-based diacid is preferably 2, 5-furandicarboxylic acid.

3. The PBAT material of claim 1 or 2, characterized in that the preparation of the prepolymer a comprises: mixing the bio-based dibasic acid with the butanediol, and polymerizing to form the prepolymer A under the action of a titanium catalyst or an antimony catalyst; 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 3-6 wt% of the total weight of the bio-based dibasic acid and the butanediol.

4. The PBAT material of any of claims 1 to 3, wherein the prepolymer A has a number average molecular weight of 1000 to 2000 g/mol and a viscosity of 0.15 to 0.20 dL/g.

5. The PBAT material of any of claims 1-4, wherein the PBAT material has a number average molecular weight of 150000-250000 g/mol and a viscosity of 0.71-0.85 dL/g.

6. The method for preparing a high barrier and degradable PBAT material according to any of claims 1 to 5, wherein the PBAT material is prepared by copolymerizing prepolymer A with prepolymer B and 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 2000-3000 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 3000-5000 g/mol, and the viscosity of the prepolymer C is 0.28-0.45 dL/g.

9. The method according to claim 7 or 8, wherein the chain extender is one or more selected from the group consisting of a chain extender Joncryl ADR-4368, a chain extender SAG-005, a chain extender SAG-008, 2, 4-toluene diisocyanate, succinic anhydride, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate phthalic anhydride, 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline), and isohexide-2, 5-bis (2-oxazoline) in an amount of 0.5 to 5 wt.% based on the total weight of the prepolymer A, the prepolymer B, and the prepolymer C.

10. Use of a high barrier and degradable PBAT material according to any of claims 1-5 for the preparation of a film article.

Technical Field

The invention relates to the field of functional polymer materials, in particular to a high-barrier and degradable PBAT material, a preparation method thereof and application thereof in preparing a membrane product.

Background

In recent years, with the regulation and control of national environmental protection policies, more and more degradable products enter the market and come to thousands of households. Especially in the application field of polymer materials such as disposable packaging bags, shopping bags and the like, the attention on degradable materials is getting higher and higher due to the fact that white pollution is more and more serious.

PBAT materials are gaining increasing consumer and market favor due to their superior degradability. However, due to the structure of the PBAT material itself, the barrier properties of the PBAT material are naturally deficient compared to materials such as nylon and polyvinylidene chloride.

Therefore, the development of a degradable PBAT material with good barrier property is urgently needed to further expand the application range of the PBAT material and meet the application requirements of the PBAT material in various high-barrier fields.

Disclosure of Invention

In order to remedy the deficiencies of the prior art, it is an object of the present invention to provide a high barrier and degradable PBAT material which is modified to significantly improve its barrier properties and which is also highly degradable.

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 high-barrier and degradable PBAT material provided by the invention is added with a prepolymer A formed by bio-based dibasic acid and butanediol in the preparation process, wherein the bio-based dibasic acid is one or more of 2, 5-furandicarboxylic acid, succinic acid and 1, 9-azelaic 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 molar ratio of the bio-based diacid to the butanediol is 1:1 to 1.5. In some more preferred embodiments, the molar ratio of the bio-based diacid to the butanediol is 1:1 to 1.2.

In some preferred embodiments, the bio-based diacid is 2, 5-furandicarboxylic acid.

In some preferred embodiments, the prepolymer a is prepared by a process comprising: and mixing the bio-based dibasic acid with the butanediol, 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 both 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 amount of the titanium-based catalyst or the antimony-based catalyst is 3 to 6 wt% of the total weight of the bio-based dibasic acid and the butanediol

In some further preferred embodiments, during the preparation of the prepolymer a, the polymerization reaction is performed at a reaction temperature of 230 to 250 ℃ and a reaction pressure of 0.5 to 2 MPa, and the polymerization reaction is performed in a nitrogen environment.

In some preferred embodiments, the prepolymer A has a number average molecular weight of 1000 to 2000 g/mol and a viscosity of 0.15 to 0.20 dL/g.

In some preferred embodiments, the PBAT material has a number average molecular weight of 150000 to 250000 g/mol and a viscosity of 0.71 to 0.85 dL/g. In some more preferred embodiments, the PBAT material has a number average molecular weight of 150000 to 160000 g/mol and a viscosity of 0.71 to 0.78 dL/g.

The invention also provides a preparation method of the high-barrier 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 from 0.5 to 1.5: 4 to 5.5, including but not limited to the weight ratio of prepolymer a, prepolymer B, prepolymer C is from 1:5:4, 1.5: 4.5:4, 0.5: 5.5: 4, 1.5: 4: 4.5, 1.3:4.5:4.2, 0.8:5.2:4, and the like.

In some preferred embodiments, the prepolymer C accounts for less than 50 wt.% of the total weight of the prepolymer a, the prepolymer B, and the prepolymer C, and the amount of prepolymer C is controlled to ensure degradability of the PBAT material produced.

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 2000-3000 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 3-6 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 220 to 250 ℃ and a reaction pressure of 1 to 2 MPa, and the polymerization reaction is performed in a nitrogen environment.

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 3000-5000 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 3-6 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 220 to 250 ℃ and a reaction pressure of 1 to 2 MPa, and the polymerization reaction is performed in a nitrogen environment.

In some preferred embodiments, the chain extender is one or more of the chain extender Joncryl ADR-4368, chain extender SAG-005, chain extender SAG-008, 2, 4-toluene diisocyanate, succinic anhydride, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate phthalic anhydride, 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline), isohexide-2, 5-bis (2-oxazoline) in an amount of 0.5 to 5 wt.% o, based on the total weight of prepolymer a, prepolymer B, and prepolymer C.

The invention also provides application of the high-barrier and degradable PBAT material in any technical scheme in preparation of a film product.

The PBAT material provided by the invention has better barrier property through modification, is obviously superior to common commercially available membrane-grade PBAT materials, also retains excellent degradability, has wider application range compared with the existing PBAT materials, is especially suitable for membrane products, and has 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 high-barrier, degradable PBAT

The preparation steps are as follows:

(1) mixing 2, 5-furandicarboxylic acid and butanediol according to a molar ratio of 1:1.15, adding 3 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, detecting an extraction sample, and sealing the prepolymer serving as prepolymer A for later use, wherein the number average molecular weight of the prepolymer is about 1000 g/mol, and the viscosity of the prepolymer is about 0.15 dL/g.

(2) Mixing terephthalic acid and butanediol according to a molar ratio of 1:1.2, adding 3.5 per thousand of antimony trioxide catalyst, reacting for 4-5 h at 230 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, wherein the number average molecular weight of a prepolymer is about 2000 g/mol, the viscosity is about 0.15 dL/g, and sealing for later use as a prepolymer B.

(3) Mixing adipic acid and butanediol according to a molar ratio of 1:1.05, adding 4 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 3000 g/mol and the viscosity of about 0.28 dL/g, and sealing for later use as prepolymer C.

(4) A, B, C three prepolymers are mixed according to the weight ratio of 1:5:4, the mixture is vacuumized to 100 pa at 250 ℃, the proportion of the added chain extender SAG-008 is 3.5 percent, the stirring speed is 80 rpm, the mixture is reacted for 5 hours, and then the mixture is extruded and granulated to obtain high-barrier and degradable PBAT particles, wherein the number average molecular weight of the PBAT particles is 150000 g/mol, and the viscosity of the PBAT particles is 0.78 dL/g.

Pressing the granules for 5 min at 260 ℃ and 3000 Kg of pressure to prepare a membrane with the thickness of about 80 μm, and then testing the barrier property of the membrane with the same thickness prepared by a commercial membrane-grade PBAT under the same conditions according to the requirements of GB/T19789-containing and GB/T30412-containing materials 2013, and comparing the barrier property. The results are shown in Table 1.

TABLE 1

The results in table 1 show that the membrane prepared from the PBAT modified material prepared in example 1 of the present invention has good barrier properties, and both the oxygen permeability and the water vapor permeability are significantly better than those of the conventional PBAT membrane.

Example 2 preparation of high-barrier, degradable PBAT

The preparation steps are as follows:

(1) mixing 2, 5-furandicarboxylic acid and butanediol according to a molar ratio of 1:1.12, adding 3 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃, in a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with a number average molecular weight of about 2000 g/mol and a viscosity of about 0.20 dL/g, and sealing for later use as prepolymer A.

(2) Mixing terephthalic acid and butanediol according to a molar ratio of 1:1.15, adding 3.5 per thousand of antimony trioxide catalyst, reacting for 4-5 h at 230 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 3000 g/mol and the viscosity is 0.40 dL/g, and sealing the prepolymer as a prepolymer B for later use.

(3) Mixing adipic acid and butanediol according to a molar ratio of 1:1.1, adding 4 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 5000 g/mol and the viscosity of about 0.45 dL/g, and sealing for later use as prepolymer C.

(4) A, B, C three prepolymers are mixed according to the weight ratio of 1.3:4.5:4.2, the mixture is vacuumized to 100 pa at 250 ℃, the proportion of the added chain extender SAG-005 is 2%, the stirring speed is 80 rpm, the mixture is reacted for 5 hours, and then the mixture is extruded and granulated to obtain high-barrier and degradable PBAT particles, wherein the number average molecular weight of the PBAT particles is 160000 g/mol, and the viscosity of the PBAT particles is 0.77 dL/g.

Pressing the granules for 5 min at 260 ℃ and 3000 Kg pressure to prepare a membrane with the thickness of about 80 μm, and then testing the barrier property of the membrane with the same thickness prepared by common commercial membrane-grade PBAT according to the requirements of GB/T19789-2005 and GB/T30412-2013 under the same conditions, and comparing. The results are shown in Table 2.

TABLE 2

The results in table 2 show that the membrane prepared from the PBAT modified material prepared in example 2 of the present invention has a better barrier property, and both the oxygen permeability and the water vapor permeability are significantly better than those of the conventional PBAT membrane.

Example 3 preparation of high-barrier, degradable PBAT

The preparation steps are as follows:

(1) mixing 2, 5-furandicarboxylic acid and butanediol according to a molar ratio of 1:1.05, adding 3 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃, in a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 1500 g/mol and the viscosity of about 0.18 dL/g, and sealing the prepolymer as prepolymer A for later use.

(2) Mixing terephthalic acid and butanediol according to a molar ratio of 1:1.1, adding 3.5 per thousand of antimony trioxide catalyst, reacting for 4-5 h at 230 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 2200 g/mol and the viscosity of about 0.20 dL/g, and sealing for later use as a prepolymer B.

(3) Mixing adipic acid and butanediol according to a molar ratio of 1:1.15, adding 4 per thousand of antimony trioxide catalyst, reacting for 3-4h at 240 ℃ under a nitrogen environment and under a pressure of 1.5 Mpa, extracting a sample, detecting, obtaining a prepolymer with the number average molecular weight of about 3300 g/mol and the viscosity of about 0.32 dL/g, and sealing for later use as prepolymer C.

(4) A, B, C three prepolymers are mixed according to the weight ratio of 0.8:5.2:4.0, the mixture is vacuumized to 100 pa at 250 ℃, the chain extender 1, 4-phenyl-bis (2-oxazoline) is added, the proportion is 2.5%, the stirring speed is 80 rpm, the reaction is carried out for 5 hours, and then the extrusion granulation is carried out, thus obtaining the high-barrier and degradable PBAT particle, the number average molecular weight of which is 155000 g/mol, and the viscosity of which is 0.79 dL/g.

Pressing the granules for 5 min at 260 ℃ and 3000 Kg pressure to prepare a membrane with the thickness of about 80 μm, and then testing the barrier property of the membrane with the same thickness prepared by a commercially available common membrane-grade PBAT according to the requirements of GB/T19789-2005 and GB/T30412-2013 under the same conditions, and comparing. The results are shown in Table 3.

TABLE 3

The results in table 3 show that the membrane prepared from the PBAT modified material prepared in example 3 of the present invention has better barrier properties, and both the oxygen permeability and the water vapor permeability are significantly better than those of the conventional PBAT membrane.

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.