阅读说明：本技术 一种生物降解可控的生物基聚酯热塑性弹性体及其制备方法 (Biodegradable controllable bio-based polyester thermoplastic elastomer and preparation method thereof ) 是由 袁皓 东为富 王世波 李婷 王艺杰 汪洋 于 2020-07-07 设计创作，主要内容包括：本发明提供一种生物降解可控的生物基聚酯热塑性弹性体及其制备方法,属于生物基聚酯热塑性弹性体制备领域。所述的生物基聚酯热塑性弹性体的聚合单体包括：(A)脂肪族二元酸及其酸酐、二酯、酰卤的一种或多种；(B)不饱和脂肪酸及其多聚体以及其酸酐、酰卤的一种或多种；(C)芳香族或杂环二元酸及其酸酐、二酯、酰卤的一种或多种；(D)脂肪族二元醇及其二缩水甘油醚的一种或多种；该种生物降解可控的生物基共聚酯热塑性弹性体由上述单体(A)、(B)、(C)与(D)在催化剂条件下进行酯化,再通过熔融缩聚或界面聚合制备得到。本发明一步法制备的生物基聚酯热塑性弹性体分子量高、生物降解可控、机械性能优异。(The invention provides a biodegradable controllable bio-based polyester thermoplastic elastomer and a preparation method thereof, belonging to the field of preparation of bio-based polyester thermoplastic elastomers. The polymerized monomers of the bio-based polyester thermoplastic elastomer comprise: (A) aliphatic dibasic acid and one or more of anhydride, diester and acyl halide thereof; (B) unsaturated fatty acid and its polymer and one or more of its anhydride, acyl halide; (C) aromatic or heterocyclic diacid and one or more of anhydride, diester and acyl halide thereof; (D) one or more of aliphatic dihydric alcohol and diglycidyl ether thereof; the biodegradable controllable bio-based copolyester thermoplastic elastomer is prepared by esterifying the monomers (A), (B), (C) and (D) under the condition of a catalyst and then carrying out melt polycondensation or interfacial polymerization. The bio-based polyester thermoplastic elastomer prepared by the one-step method has high molecular weight, controllable biodegradation and excellent mechanical property.)

1. A biodegradable controlled bio-based polyester thermoplastic elastomer, wherein the polymerized monomers of the bio-based polyester thermoplastic elastomer comprise:

a: one or more than two of aliphatic dibasic acid, anhydride, diester and acyl halide thereof are mixed;

b: unsaturated fatty acid and its polymer, acid anhydride, acyl halide or a mixture of two or more of them;

c: aromatic or heterocyclic dibasic acid and one or more than two of anhydride, diester and acyl halide thereof;

d: one or more than two of aliphatic dihydric alcohol and diglycidyl ether thereof;

the biodegradable controllable bio-based polyester thermoplastic elastomer is prepared by esterifying the monomer A, B, C and D under the condition of a catalyst and then carrying out melt polycondensation or interfacial polymerization.

2. The biodegradation controlled bio-based polyester thermoplastic elastomer according to claim 1, wherein the molar ratio of the total of the polymerized monomers A, B, C to the polymerized monomers D is 1:1 to 2; the molar ratio of the polymerized monomer C to the total polymerized monomer A, B, C is 60% or less.

3. The biodegradable controllable bio-based polyester thermoplastic elastomer as claimed in claim 1, wherein the number average molecular weight of the bio-based polyester thermoplastic elastomer is 10000-70000 g/mol, and the molecular weight distribution is 1.5-4.

4. The biodegradation of the controlled biodegradable biobased polyester thermoplastic elastomer of claim 1 wherein the melt index of the biobased polyester thermoplastic elastomer is 3 to 50g/10min and the carboxyl end groups are 5 to 80mol/t.

5. The biodegradable controlled bio-based polyester thermoplastic elastomer as claimed in claim 1, wherein Shore A hardness of the bio-based polyester thermoplastic elastomer is 50-95.

6. The biodegradation controlled bio-based polyester thermoplastic elastomer according to claim 1, wherein the tensile set of the bio-based polyester thermoplastic elastomer is 10 to 300%.

7. The biodegradation controlled bio-based polyester thermoplastic elastomer according to any one of claims 1 to 6, wherein said polymeric monomer A is one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, lauric acid, maleic acid, fumaric acid, itaconic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, and their anhydrides, diesters, and diacyl halide derivatives; the polymeric monomer B is one or more of oleic acid, linoleic acid, linolenic acid, arachidonic acid, 20-carbon-5-olefine acid, 22-carbon-6-olefine acid and polymer thereof, acid anhydride and acyl halide derivatives.

8. The controlled biodegradation biobased polyester thermoplastic elastomer according to any one of claims 1 to 6, wherein said monomer C is one or a mixture of two or more of terephthalic acid, phthalic acid, isophthalic acid, 1, 4-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, 1, 8-naphthalene dicarboxylic acid, 2, 5-furandicarboxylic acid and its anhydride, diester, dihalide derivatives; the monomer D is ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, dimer fatty alcohol, dipropylene glycol, polyoxyethylene, polyethylene glycol, polypropylene glycol and their diglycidyl ether.

9. The method for preparing a controlled biodegradation biobased polyester thermoplastic elastomer according to any one of claims 1 to 8 wherein the steps of the method are as follows:

(1) uniformly mixing the polymerized monomers A, B, C, D, adding 0.01-0.5% of catalyst by mass percent for esterification reaction, and completing the esterification stage when the collection system is not in the presence of water;

(2) then, the polycondensation reaction is carried out, and when the stirring current of the polycondensation motor does not rise any more, namely the viscosity of the product is maximum, the polycondensation stage is finished.

10. The preparation method of claim 9, wherein the esterification reaction temperature is 100-260 ℃ and the esterification reaction time is 1-3 h; the temperature of the polycondensation reaction is 100-250 ℃, the vacuum degree of the polycondensation reaction is 20-4000 pa, and the polycondensation reaction time is 2-5 h; the reaction catalyst in the step (1) is one or more of Lewis acid, germanium compounds, antimony compounds, titanium compounds, zinc compounds and tin compounds.

Technical Field

The invention relates to a biodegradable controllable bio-based polyester thermoplastic elastomer and a preparation method thereof, in particular to a high molecular weight biodegradable controllable bio-based polyester thermoplastic elastomer with excellent mechanical properties and a preparation method thereof.

Background

The polyester thermoplastic elastomer has rubber elasticity and plastic processability, has high strength, good flex fatigue resistance, excellent chemical resistance, excellent flexibility and dynamic performance, wide application temperature range, excellent impact resistance at low temperature and excellent creep resistance at high temperature, can be applied to the field of molded products with high toughness, flex resistance and medium heat resistance and chemical resistance, and also has important functions in the aspects of polymer toughening and compatibilization. Currently, the polyester thermoplastic elastomers commercialized are Akzo Plastics to SDM

Of DupontOf Eastman chemical

Of EniChem Elastomeri

Of ToyoboOf Nippon Zeon

Of ElanaOf General Electric

Of Hoechst Celanese

And

at present, the global pollution problem of micro plastic is more and more serious, and the problems that petroleum resources cannot be regenerated and the like limit the long-term development of the current plastic materials. Therefore, in order to reduce the dependence on petroleum resources and broaden the application of polyester thermoplastic elastomers in the field of disposable plastic products, it is necessary to develop a bio-based polyester thermoplastic elastomer with high molecular weight, controllable biodegradation and excellent mechanical properties.

In chinese patent applications CN105001400A and CN104497318A, a series of methods for preparing aliphatic biodegradable thermoplastic elastomers are disclosed: the elastomer is prepared by synthesizing oligomers with different properties and then carrying out chain extension or ester exchange. The raw materials used in the preparation method of the aliphatic biodegradable thermoplastic elastomer are isocyanate, the substances are toxic and expensive, the generation cost of the materials is increased, and in addition, the aliphatic biodegradable thermoplastic elastomer has a fast degradation period and is uncontrollable in degradation.

In summary, the polyester thermoplastic elastomers commercialized at present are petroleum-based products, and the elastomers are not biodegradable and have an influence on the environment after being discarded. Although there are patents related to the preparation method of aliphatic biodegradable thermoplastic elastomer, the preparation process is not environment-friendly, the production cost is high, and the degradation period is not controllable.

Disclosure of Invention

The term "bio-based" refers to that renewable biomass and non-grain lignocellulose agricultural and forestry waste are used as raw materials and are prepared by biological, chemical and physical methods and the like.

Aiming at the problems in the prior art, the invention has the advantage that the bio-based polyester thermoplastic elastomer with high molecular weight, controllable biodegradation and excellent mechanical property is prepared by adopting a one-step method.

The technical process for preparing the biodegradable controllable bio-based polyester thermoplastic elastomer comprises the following steps:

a biodegradable controlled bio-based polyester thermoplastic elastomer, the polymeric monomers of which comprise:

a: aliphatic dibasic acid and one or more of anhydride, diester and acyl halide thereof;

b: unsaturated fatty acid and its polymer and one or more of its anhydride, acyl halide;

c: aromatic or heterocyclic diacid and one or more of anhydride, diester and acyl halide thereof;

d: one or more of aliphatic dihydric alcohol and diglycidyl ether thereof;

the biodegradable controllable bio-based copolyester thermoplastic elastomer is prepared by esterifying the monomers (A), (B), (C) and (D) under the condition of a catalyst and then carrying out melt polycondensation or interfacial polymerization.

Specifically, the polymerization of the bio-based degradable copolyester thermoplastic elastomer comprises the following steps:

(1) uniformly mixing the monomer A, B, C and the monomer D, adding 0.01-0.5 mass percent of catalyst for esterification reaction at the reaction temperature of 100-260 ℃, finishing the esterification stage when no water is generated in a collection system, and reacting for 1-3 hours;

(2) and (3) performing polycondensation reaction at the reaction temperature of 100-250 ℃ and the reaction vacuum degree of 20-4000 pa, and finishing the polycondensation stage when the stirring current of a polycondensation motor does not rise any more, namely the viscosity of the product is maximum, wherein the reaction time is 2-5 h.

The reaction catalyst in the step (1) is one or more compounds of Lewis acid, germanium compounds, antimony compounds, titanium compounds, zinc compounds and tin compounds.

The mole ratio of the total polymerized monomer A, B, C to the polymerized monomer D in the biodegradation controlled bio-based polyester thermoplastic elastomer is 1: 1-2; the molar ratio of the polymerized monomer C to the total polymerized monomer A, B, C is 60% or less.

The biodegradable controllable bio-based polyester thermoplastic elastomer is characterized in that the number average molecular weight of the elastomer is 10000-70000 g/mol, and the molecular weight distribution is 1.5-4; the melt index is 3-50 g/10min, and the carboxyl end group is 5-80 mol/t.; the Shore hardness A is 50-95; the permanent tensile set is 10 to 300%.

The above-mentioned polymeric monomer A is selected from C₂～C₁₆Aliphatic dibasic acids and their anhydrides, diesters, and diacid halide derivatives, preferably selected from one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, lauric acid, maleic acid, fumaric acid, itaconic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, and the like, and their anhydrides, diesters, and diacid halide derivatives, most preferably from one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and their anhydrides, diesters, and diacid halide derivatives.

The polymeric monomer B is one or more of oleic acid, linoleic acid, linolenic acid, arachidonic acid, 20-carbon-5-olefine acid, 22-carbon-6-olefine acid and polymer thereof, and acid anhydride and acyl halide derivatives.

The monomer C is one or more of terephthalic acid, phthalic acid, isophthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 5-furandicarboxylic acid, etc., and acid anhydride, diester, and dihalide derivatives thereof.

The above-mentioned monomer D is selected from C₂～C₁₀Aliphatic diols and their diglycidyl ethers, preferably selected from ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1,9-nonanediol, 1, 10-decanediol, dimer fatty alcohol, dipropylene glycol, polyoxyethylene, polyethylene glycol, polypropylene glycol and one or more of their diglycidyl ethers, most preferably ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol.

Compared with the prior art, the invention has the beneficial effects that:

(1) the polymerization monomers of the polyester thermoplastic elastomer prepared by the invention are nontoxic, and part or all of the polymerization monomers are bio-based raw materials, so that the consumption of petroleum resources is reduced, and the polyester thermoplastic elastomer belongs to environment-friendly materials.

(2) The polyester thermoplastic elastomer prepared by the invention has high molecular weight and excellent mechanical property, and the degradation period of the material can be regulated and controlled by adjusting the monomer proportion.

(3) The polymerization process is simple, the one-step preparation method is adopted, the industrial production can be realized, and the prepared polyester thermoplastic elastomer is excellent and stable in quality.

Detailed Description

The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.

The molecular weight and the molecular weight distribution of the polymer are determined by adopting a gel permeation chromatography, chloroform is used as a solvent, a Waters-1525u instrument is used for testing, and polystyrene is used as a standard sample.

The carboxyl end groups of the polymer are tested by an acid-base titration method according to the method A in GB/T14190-. The mixed solution is phenol-trichloromethane with the volume ratio of 2: 3. The standard titration solution is potassium hydroxide-benzyl alcohol, the concentration is 0.01mol/L, and the standard titration solution is configured and calibrated according to 4.24 in GB/T601-2002. The bromophenol blue indicator concentration was 0.2%. Test preparation: 0.5g of the sample was dissolved in 25.00ml of a phenol-chloroform mixed solvent.

The melt index of the polymer was measured by a melt index meter according to GB/T3682-2000 rule A under test conditions D (temperature: 190 ℃ C., load 2.16 kg).

Tensile properties of the polymers were tested according to GB/T17037.1-1997, using the type A abrasive tool of GB/T17037.1-1997 to prepare specimens conforming to type 1A of GB/T1040.2-2006. The conditioning of the sample is carried out according to the regulations GB/T2918-. The test was carried out as specified in GB/T1040.2-2006, with a test rate of 50 mm/min.