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A kind of preparation method of rigid polyimide foam material

A technology of polyimide and foam materials, which is applied in the field of polymer material preparation, can solve the problems of difficult large-scale preparation, poor bonding performance between microspheres, and reduced thermal oxidation resistance, etc., to achieve easy realization Effects of scale, abundant candidate raw materials, and cost reduction

Active Publication Date: 2021-08-10
AEROSPACE RES INST OF MATERIAL & PROCESSING TECH +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Rigid polyimide foams that have been commercialized are based on 3,3',4,4'-benzophenone tetra-acid dianhydride (BTDA) and 4,4'-diaminodiphenyl ether (4,4 '-ODA) made of serialized foam products (TEEK-LL), based on 3,3',4,4'-diphenyl ether tetra-acid dianhydride (ODPA) and 4,4'-ODA made of serialized Foam products (TEEK-HH) and TEEK-CL series products based on BTDA and diaminodiphenyl sulfone (DDS). These foam materials are molded by compression molding, and often have poor bonding performance between microspheres. As a result, the compressive strength of the foam is low, and the closed cell rate is not high
[0006] Chinese patent CN102964834A discloses a new method for preparing rigid foam, which uses norbornene anhydride as an end-capping agent to prepare a polyimide resin with a norbornene structure in the main chain, and then utilizes it in the curing and crosslinking process In this system, the released gas expands and foams. The non-aromatic ring conjugated structure is introduced into the system, which reduces the thermal oxidation resistance of the foam when it is used at high temperature for a long time. At the same time, the raw materials prepared by this method are mostly isomers. Mainly biphenyl dianhydride, the cost is extremely high, and it is difficult to realize large-scale preparation on a large scale

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Method for preparing a hard polyimide foam material, the method comprising the steps of:

[0031] A. The dried 3, 3 ', 4,4'-diphenyl ether tetrahydride 31 g is added to a mixed solvent containing 60 g of tetrahydrofuran and 12.8 g of methanol, warmed to 60 ° C, while stirring for 3 h after cooling to room temperature, 41 g 2,2-double [4- (4-aminopenzoxy) phenyl] propane (BAPP) was added, and then 3.6 gak8805 was added to 60 ° C for 2 h, and 3.6 gak8805 was added, and the precursor solution was obtained.

[0032] B. Treatment of the precursor solution in an oven at 90 ° C, then pulverized into a 120 ° C oven for foaming, duration of 60 min;

[0033] c, the above-mentioned foam is hot, the hot press temperature is 130 ° C, the compressive strength is 10 MPa, and then the sample is placed in a mold of 320 ° C, the closed mold is foamed, the foaming time is maintained for 2 h, then naturally cooling to room temperature, thus Get a hard polyimide foam;

[0034] The material has ...

Embodiment 2

[0037] Method for preparing a hard polyimide foam material, the method comprising the steps of:

[0038] A. The dried 3, 3 ', 4,4'-diphenyl ether tetrahydride 31 g is added to a mixed solvent containing 60 g of tetrahydrofuran and 12.8 g of methanol, warmed to 60 ° C, while stirring for 3 h after cooling to room temperature, 41 g 2,2-double [4- (4-aminopenzoxy) phenyl] propane (BAPP) was added, and then 3.6 gak8805, 3.6 g of foaming auxiliaries were added to 60 ° C for 2 h, which was added to obtain a precursor solution. ;

[0039] B, the precursor solution was treated in an oven at 85 ° C, and then pulverized into a 120 ° C oven for foaming, duration of 60 min;

[0040] c, the above-mentioned foam is hot, the hot press temperature is 130 ° C, the compressive strength is 10 MPa, and then the sample is placed in a mold of 320 ° C, the closed mold is foamed, the foaming time is maintained for 2 h, then naturally cooling to room temperature, thus Get a hard polyimide foam;

[0041] Th...

Embodiment 3

[0043] Method for preparing a hard polyimide foam material, the method comprising the steps of:

[0044] A. The dried 3, 3 ', 4,4'-diphenyl ether tetrahydride 32.2 g of a mixed solvent containing 50 g of tetrahydrofuran and 12.8 g of methanol was added, warmed to 60 ° C, and the temperature was stirred for 3 h after cooling to room temperature. To add 29.2 g of 1,3-bis (4'-amine-based phenoxy) benzene (1,3,4-APB), and then increasing 3.6 gak8805, 7.0 g of foaming auxiliaries, discharged from 60 ° C for 2 h. Get the precursor solution;

[0045] B, the precursor solution was treated in an oven at 90 ° C, and then pulverized into a 100 ° C oven for foaming, duration of 30 min;

[0046] c, the above-mentioned foam is hot, the hot press temperature is 110 ° C, the compressive strength is 10 MPa, and then the sample is placed in a mold of 300 ° C, the shutdown is foamed, the foaming time is maintained for 2 h, then naturally cooling to room temperature, thus Get a hard polyimide foam;

...

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Abstract

The invention relates to a rigid polyimide foam material and a preparation method thereof, and belongs to the technical field of preparation of polymer polyimide foam materials. Add aromatic dianhydride into tetrahydrofuran / aliphatic alcohol mixed solvent, heat to dissolve; add aromatic diamine to react to form foam precursor solution after the solution is transparent, then add foam stabilizer, foaming aid, and mix well; The above solution is placed in an oven to remove the solvent, and then the temperature is raised for primary foaming; the first foamed product is molded to a compact state, and the temperature is further raised for secondary foaming to obtain a polyimide foam. The method has the characteristics of low preparation cost, abundant candidate raw materials, and easy scale-up; the foam material prepared by the present invention has uniform cell structure, adjustable apparent density, high compressive strength, high closed cell ratio, and almost no slag drop specialty.

Description

Technical field [0001] The present invention relates to a hard polyimide foam material and a preparation method thereof, belonging to the preparation of polymer material, and the hard foam refers to no flexibility, large compression strength, and the stress can generate a variable. The foam material that cannot be returned to the original state after the stress is released. Background technique [0002] Polyimide foam material is a high performance foam material having good mechanical properties, excellent flame retardant properties, and anti-fire, compared to other types of foam, and does not produce harmful gases during use. The performance adjustment range is wide, easy to install and disassemble, while high temperature resistance, it also has excellent low-temperature resistance, has been used as insulation, and noise reduction materials have been widely used abroad. [0003] The hard polyimide foam is one of the polyimide foam, which can be used to prepare a hard polyimide f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/10C08J9/04C08L79/08
CPCC08G73/1071C08J9/04C08J2379/08
Inventor 马晶晶酒永斌赵一搏滕冲熊春晓许小强马晓静
Owner AEROSPACE RES INST OF MATERIAL & PROCESSING TECH