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A kind of crystalline thermoplastic copolymerized polyimide resin and its application

A polyimide resin, thermoplastic technology, applied in crystalline thermoplastic copolyimide resin and its application field, can solve the problems of processing temperature exceeding 400 ℃, high melting point and melt viscosity, poor melt crystallization ability, etc. Achieve excellent melt crystallinity, lower melt viscosity, and easy melt processability

Active Publication Date: 2018-08-31
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, there are very few polyimide resins with both crystallinity and melt processability, mainly because the prior art mainly has the following disadvantages: (1) the rigid structure of the molecular chain of polyimide and the strong interaction between molecules lead to its melting point And the melt viscosity is too high, the processing temperature often exceeds 400°C, and the processing is difficult
(2) Most crystalline polyimides lose or greatly reduce their crystallization ability after melting, and the parts cannot show high temperature resistance
(3) Even if a small number of polyimides still show crystallization ability after melting, their crystallization rate is very slow, and the parts need to undergo a long period of high-temperature post-treatment to show crystallinity
However, the crystallization ability of the polymer melt is poor, and it is necessary to add a low-molecular nucleating agent or carbon nanofiller as a nucleating agent to show repeated crystallinity, and cannot be used directly as a crystalline resin.
At the same time, in order to obtain crystalline polyimide with a lower melting point and a higher glass transition temperature in the above-mentioned documents, monomers with low versatility, difficulty in synthesis, and high specificity have to be used, resulting in higher raw material costs and difficult Realize mass production and form products with market competitiveness
[0008] In summary, in the prior art, most of the crystalline polyimides with a glass transition temperature greater than 190°C and a melting point lower than 385°C with a fully aromatic structure have the disadvantages of poor melt crystallization ability and high melt viscosity

Method used

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  • A kind of crystalline thermoplastic copolymerized polyimide resin and its application
  • A kind of crystalline thermoplastic copolymerized polyimide resin and its application
  • A kind of crystalline thermoplastic copolymerized polyimide resin and its application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Add 11.6930g (40.0mmol) 1,3-bis(4-aminophenoxy)benzene (abbreviated as TPER) to a three-necked flask equipped with a stirrer, reflux condenser and nitrogen gas guide tube, 46.7730g (160.0mmol) 1,4-bis(4-aminophenoxy)benzene (abbreviated as TPEQ), 77.2440g (192.0mmol) 3,3',4,4'-triphenylene ether tetracarboxylic dianhydride (abbreviated as HQDPA), 2.3700g (16.0mmol) phthalic anhydride (abbreviated as PA), 526g m-cresol, 30 drops of isoquinoline, react under nitrogen atmosphere, stir evenly, heat up to 200°C for 8 hours, cool to room temperature, Ethanol was added as a precipitating agent, and the polymer was precipitated in powder form, washed with a large amount of ethanol and water, and then dried in a vacuum oven at 150° C. for 10 hours to obtain polyimide resin PI-1.

[0052] The inherent viscosity of PI-1 measured by an Ubbelohde viscometer in a m-cresol solution with a concentration of 0.5 g / dL at 30°C is 0.59 dL / g.

[0053] The X-ray powder diffraction pattern of...

Embodiment 2

[0057] Add 2.3386g (8.0mmol) TPER, 3.5080g (12.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, 53g of m-cresol and 5 drops of isoquinoline were reacted under a nitrogen atmosphere, stirred evenly, heated to 200°C for 8 hours, cooled to room temperature, and ethanol was added as a precipitating agent, and the polymer was precipitated in powder form. Using a large amount of ethanol and washed with water, and then dried in a vacuum oven at 150° C. for 10 hours to obtain polyimide resin PI-2.

[0058] The obtained polyimide PI-2 was measured by DSC, as a result, a double melting peak T was observed in the first heating curve m at 340°C and 368°C, no clear observation of T g and T c (with a high degree of crystallinity). T is observed in the second warming g at 205°C, T m 340°C and 368°C. Its 5% thermal decomposition temperature in air is measured to be 517° C., and the inherent viscosity is 0.58 dL / g. The minimum melt complex viscosity measured by rotational rh...

Embodiment 3

[0060] Add 3.5080g (12.0mmol) TPER, 2.3386g (8.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, 53g of m-cresol and 5 drops of isoquinoline were reacted under a nitrogen atmosphere, stirred evenly, heated to 200°C for 8 hours, cooled to room temperature, and ethanol was added as a precipitating agent, and the polymer was precipitated in powder form. Using a large amount of ethanol and washed with water, and then dried in a vacuum oven at 150° C. for 10 hours to obtain polyimide resin PI-3.

[0061] The obtained polyimide PI-3 was measured by DSC, and the result was a double melting peak T in the first heating curve. m at 338°C and 364°C, no clear observation of T g and T c(with a high degree of crystallinity). T is observed in the second warming g 201°C, T m 339°C and 362°C. Its 5% thermal decomposition temperature in air is measured to be 520° C., and the inherent viscosity is 0.56 dL / g. The minimum melt complex viscosity measured by rotational rheometer is...

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Abstract

The invention discloses crystalline thermoplastic copolyimide resin. The crystalline thermoplastic copolyimide resin is prepared through condensation polymerization of an aromatic dianhydride monomer, an aromatic diamine monomer and an end-capping reagent. 4-bis(3,4-dicarboxyphenoxy)benzene dianhydride or 2,2',3,3'-triphenyl diether tetracarboxylic dianhydride serves as the aromatic dianhydride monomer, 4,4'-(1,3-phenylenedioxy)dianiline is mixed with common aromatic diamine to serve as the aromatic diamine monomer, and phthalic anhydride serves as the end-capping reagent. The copolyimide resin has high glass-transition temperature, high thermal stability, low melt viscosity, excellent melt repeated crystallization capacity and high melt processability, and melting point range is 300-380 DEG C. The polymer can be widely applied to preparation of composite material matrix resin, high-temperature adhesive, powder paint, high-performance films, polymer powder for 3D printing and other materials.

Description

technical field [0001] The invention relates to a polyimide resin, in particular to a crystalline thermoplastic copolymerized polyimide resin and its application. Background technique [0002] Polyimide resin is currently one of the highest heat-resistant polymer materials in industrial practical applications. Due to its comprehensive properties such as high thermal stability, solvent resistance, high mechanical strength, excellent insulation, and radiation resistance, it has been Widely used in aerospace, mechanization, electrical and electronic fields. Due to the rigid molecular chain and the strong interaction force between molecules, polyimide is difficult to dissolve and melt. Therefore, most polyimide resins can only be processed by solution molding and hot pressing, and cannot be used in engineering. Extrusion and injection molding (hereinafter referred to as melt processing) are commonly used in plastics. Melt processing has the advantages of one-time molding of co...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/10
CPCC08G73/1071
Inventor 方省众张鸿飞王玮陈国飞
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI