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Shape memory polyether ester as well as preparation method and application thereof

A polyetherester and memory technology, applied in the field of polymers, can solve the problems of excessive side reactions of 1,4-butanediol, unsatisfactory use of shape memory materials, unsuitable for synthesizing polymer materials, etc., and achieve good shape memory. effect, the effect of increasing the positive reaction rate of esterification and reducing the amount of addition

Active Publication Date: 2020-06-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] CN107973904A discloses the use of 2,5-furandicarboxylic acid dimethyl, 2,5-furandicarboxylic acid di-R1 ester and 2,5-furandicarboxylic acid di-R2 ester to replace terephthalic acid as a diacid monomer to prepare polyether ester Shape memory materials, the shape recovery rate can reach more than 80%, but dimethyl 2,5-furandicarboxylate is very expensive and is not suitable as the main monomer for synthetic polymer materials
[0005] CN106188513B discloses a method for synthesizing polyether ester block copolymers, but the amount of 1,4-butanediol used in this method is too much due to side reactions, and the amount added far exceeds the proportioning amount, resulting in a substantial increase in cost
In addition, the polyether diols used are mainly low molecular weight monomers, which have poor crystallization properties in copolyether esters and are not ideal for use as shape memory materials.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0019] The preparation method of the shape-memory polyether ester provided by the present invention comprises polymerizing aliphatic dibasic acid, aliphatic dibasic alcohol, polyether dibasic alcohol and polyol in the presence of a composite catalyst at 130-240°C until Until no small molecular fractions are distilled out, then place the obtained polymerization reaction product at 200-260°C and vacuum degree below 200Pa to carry out vacuum distillation reaction; the number-average molecular weight of the polyether diol is 1,000-10,000, so The polyhydric alcohol includes more than three alcoholic hydroxyl groups, and the complex catalyst is a mixture of an esterification catalyst and a polycondensation catalyst.

[0020] In the present invention, the terminal group of the polyether diol is a hydroxyl group, which can undergo polycondensation reaction with aliphatic dibasic acid to form a polyether chain segment. The molar ratio of the aliphatic dibasic acid to the aliphatic dihy...

specific Embodiment approach

[0024] According to a specific embodiment of the present invention, the preparation method of the shape-memory polyether ester comprises: adding aliphatic dibasic acid, aliphatic dibasic alcohol, polyether dibasic alcohol, polyhydric alcohol and compound catalyst to the reaction In the still, under an inert atmosphere, react at 130-240°C (preferably 140-230°C) for 0.1-8 hours (preferably 3-6 hours), until no small molecular fractions are distilled out; then, the Switch the reaction kettle to a vacuum distillation device, and react for 0.1 to 8 hours (preferably 2 to 5 hours) at 200 to 260 ° C (preferably 220 to 250 ° C) and a vacuum of 200 Pa or less (preferably 90 Pa or less) .

[0025] The present invention also provides the shape memory polyether ester prepared by the above method. The shape memory polyether ester is a polyaliphatic polyester-b-polyether polyether ester with a multi-arm star-shaped long-chain branched structure.

[0026] In addition, the present invention...

Embodiment 1

[0031] This example is used to illustrate the shape memory polyether ester provided by the present invention and its preparation method.

[0032] Succinic acid, 1,4-butanediol, polytetrahydrofuran (PTMG, Mn=2,000, the melting point of the polybutylene succinate segment formed by the polymerization of succinic acid and 1,4-butanediol and the melting point of PTMG The melting point difference is 72°C), pentaerythritol is added to the reactor, the molar ratio of succinic acid and 1,4-butanediol is 1:1.05, the addition of PTMG accounts for 40wt% of the total monomer weight fraction, the addition of pentaerythritol It is 0.2mol% of the molar dosage of succinic acid monomer, and a composite catalyst is added (relative to 100 parts by weight of succinic acid, the composite catalyst is composed of 0.1 parts by weight tetrabutyl titanate and 0.1 parts by weight lanthanum acetylacetonate), Under an inert atmosphere, react at 200°C for 5 hours, and no small molecular fractions will evapo...

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Abstract

The invention belongs to the field of polymers, and discloses shape memory polyether ester as well as a preparation method and application thereof. The shape memory polyether ester has a multi-arm star-shaped long branched chain structure, each arm chain comprises aliphatic polyester chain segments and polyether chain segments which are subjected to block copolymerization, wherein the aliphatic polyester chain segment is obtained by polycondensation of aliphatic dibasic acid and aliphatic dihydric alcohol, the difference between the melting point of the aliphatic polyester chain segment and the melting point of the polyether chain segment is at least 20 DEG C, the number of arms of the shape memory polyether ester is more than 3, and the number-average molecular weight of the polyether chain segment is 10,000-10,000. The shape memory polyether ester is a thermally driven shape memory polymer material, the structural unit and the transition temperature are adjustable, the shape fixing rate is greater than or equal to 80%, the shape recovery rate is greater than or equal to 80%, and the shape memory polyether ester has a very good shape memory effect. In addition, the shape memory polyether ester provided by the invention is simple and convenient to synthesize, easy to process and adjustable in conversion temperature.

Description

technical field [0001] The invention belongs to the field of polymers, and more specifically relates to a shape-memory polyether ester and a preparation method and application thereof. Background technique [0002] Shape memory polymer (shape memory polymer, SMP) is another new type of shape memory material developed after the discovery of shape memory alloy in the 1960s, and it is a kind of smart material. SMP refers to a polymer material in which a polymer product with an initial shape is deformed and fixed, and then restored to its original shape by means of external stimuli such as heating, magnetism, electricity, light, and solvents. Compared with traditional shape memory alloys and shape memory ceramics, shape memory polymer materials have sufficient raw materials, various varieties, light weight, large deformation, high recovery rate, fast driving response, low energy consumption and cost, and excellent processing performance. Advantages, so it has a wide range of ap...

Claims

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Application Information

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IPC IPC(8): C08G63/672C08G63/85C08G63/84C08L67/02
CPCC08G63/672C08G63/85C08G63/84C08L67/02
Inventor 韩翎祝桂香张伟张韬毅许宁计文希宋建会林蔚然
Owner CHINA PETROLEUM & CHEM CORP
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