CN104829835B - Preparation method of isocyanate-based polyimide foam - Google Patents
Preparation method of isocyanate-based polyimide foam Download PDFInfo
- Publication number
- CN104829835B CN104829835B CN201510193907.9A CN201510193907A CN104829835B CN 104829835 B CN104829835 B CN 104829835B CN 201510193907 A CN201510193907 A CN 201510193907A CN 104829835 B CN104829835 B CN 104829835B
- Authority
- CN
- China
- Prior art keywords
- preparation
- foam
- nco
- polyimide foam
- foaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a preparation method of isocyanate-based polyimide foam. The preparation method comprises that 1, polybasic aromatic anhydride is heated and dissolved in a polar solvent and undergoes a reaction with fatty alcohol to produce a polybasic aromatic anhydride derivative solution, 2, the polybasic aromatic anhydride derivative solution and a foam stabilizer are blended to form a white material, 3, polybasic aromatic anhydride and isocyanate undergo a reaction to produce a black material, 4, the foaming white material is immediately poured into the foaming black material at a room temperature under normal pressure, and the mixture is uniformly stirred, then is fast poured into a mold and is subjected to free foaming molding to form a foam intermediate and 5, the foam intermediate is heated and cured to form the isocyanate-based polyimide foam. The preparation method inhibits production of an amino group and an isocyanate group in foam material preparation, reduces a polyurea generation amount and improves isocyanate-based polyimide foam heat resistance, heat stability and flame resistance. The preparation method has the advantages of simple processes, excellent product comprehensive properties, and industrial production and wide application feasibility.
Description
Technical field
The present invention relates to a kind of preparation method of polymer foams, particularly a kind of NCO polyamides is sub-
The preparation method of amine foam.
Background technology
NCO polyimide foam belongs to the class in polyimide foam, due to using room temperature free foaming into
Type technique and to material purity requirement it is relatively low therefore with the polyimide foam as obtained by powder method preparation technology
Compared to obvious industrialized production advantage and market price advantage is shown, with the stronger market competitiveness.
According to patent documents such as US3300420, US4026833, US7541388, CN101812232A, CN102127225A and
The correlative theses report of Zhan Maosheng, Wang Liancai et al., the preparation method of current NCO polyimide foam mainly has two
The mode of kind：1. react to form black material with polynary fragrant acid anhydride and excess isocyanate first, then by black material with containing foam stabiliser,
Surface-active, catalyst, the combination solution mixing of foaming agent, obtain NCO polyamides sub- by quick stirring free foaming
Amine foam intermediate, eventually passes hot setting treatment and obtains NCO polyimide foam；2. first by polynary fragrance
The polar solvent solution of acid anhydride derivative obtains combination solution with foam stabiliser, surface-active, catalyst, foaming agent compounding, so
Isocyanates is mixed with combination solution again afterwards, in obtaining NCO polyimide foam by quick stirring free foaming
Mesosome, eventually passes hot setting treatment and obtains NCO polyimide foam.Involved bubble in both modes
Foam forming process depends on isocyanates with the carbon dioxide free diffusing produced by the reaction of foaming agent water to realize.But
Due to isocyanates excess in a kind of mode, therefore the amino and the isocyanates of remnants generated in free foaming forming process
Will not continue to generation polyimide precursor can form heat endurance and the poor polyureas of anti-flammability on the contrary, ultimately result in foam material
Expect that the heat resistance and anti-flammability of entirety have certain gap compared with pure polyimide foam, and it is obtained in this way
Foam densities are relatively large；Due to isocyanates not elder generation and polynary fragrant acid anhydride prepolymerization, therefore phase in the second way
Isocyanates can be more violent with the reaction of water in foamed forming process for this kind of mode for first way, generation
Amino amount and gas flow are also more, although the amino of generation can be with polynary fragrant acid anhydride derivatives reaction generation polyimides forerunner
Body, but at the same time amino also equally will can significantly drop with a large amount of unreacted NCO reaction a large amount of polyureas of generation
The overall heat resistance of oligomeric polyimide foam, heat endurance and anti-flammability, but isocyanates obtained in this way
Base Polyimide foams density is relatively low.
The content of the invention
It is an object of the invention to provide it is a kind of can suppress free foaming forming process in amino it is anti-with NCO
The preparation method of the NCO polyimide foam answered.
The object of the present invention is achieved like this：
(1) polynary fragrant acid anhydride heating for dissolving in polar solvent is reacted with fatty alcohol, obtains polynary fragrant acid anhydride derivative molten
Liquid, specially：To polar solvent and polynary fragrant acid anhydride is sequentially added in container, stir and heat, treat that emulsion temp reaches 40-
Fatty alcohol is added thereto at 50 DEG C carries out esterification, and reaction forms the derivative solution of clear after 2-3 hours；
(2) derivative solution and the foam stabiliser white material of compounding synthesis, specially：To in derivative solution under room temperature condition
Sequentially add the hair that catalyst, foam stabiliser, surfactant and deionized water were uniformly mixed and obtained clear
The white material of bubble；
(3) polynary fragrant acid anhydride is synthesized black material with isocyanates, specially：Under room temperature condition successively by polar solvent,
Polynary fragrant acid anhydride and isocyanates are added rapidly in container, access nitrogen protection device, container is placed in oil bath pan and is heated,
And stir, obtain the black material that foams after polynary fragrant anhydride reactant is complete；
(4) the white material of foaming is poured into the black material of foaming at once under room temperature condition of normal pressure, mould is poured into rapidly after stirring
Middle free foaming shaping obtains foam intermediate；
(5) foam intermediate is obtained kind of a NCO polyimide foam by being heating and curing.
The present invention can also include：
1st, the mass fraction of each component is：Aromatic dianhydride is 120-200 parts, polar solvent is 100-200 parts, fatty alcohol is
5-20 parts, foam stabiliser 10-20 parts, surfactant 10-20 parts, catalyst 5-10 parts, deionized water be 10-20 parts, it is many
Isocyanates 200-400 parts.
2nd, it is described to be heating and curing specially：The demoulding after 3-5 minutes of foam intermediate room temperature, is transferred to 240-260 DEG C
Electric drying oven with forced convection in solidify 2-3 hours.
3rd, the polynary fragrant acid anhydride is：Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-
Xenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, mellitic acid
Three acid anhydrides, the ester of three trimellitic anhydride -1,3,5- benzene three or 1,3,5- tri- oxygen-three (4- phthalic anhydrides) benzene.
4th, the polar solvent is：1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or two
Methyl sulfoxide.
5th, the fatty alcohol is：Methyl alcohol or ethanol.
6th, the foam stabiliser is：Non-hydrolytic type water soluble polyether siloxanes (AK8805, DC193, L580)；Live on surface
Property agent is：Non-ion fluorin carbon surface active agent (), polyoxyethylene nonionic table
Face activating agent (PEG-600, PEG-300, PEG-400, PEG-800, PEG-1000).
7th, the catalyst is：Triethanolamine, triethylenediamine, stannous octoate, dibutyl tin laurate or
Dabco33-LV；Foaming agent includes：Deionized water.
8th, the polyisocyanates is：Methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) or many
Phenyl polymethylene polyisocyanates (PAPI).
9th, the constant heating-up temperature of the oil bath pan is 30-70 DEG C.
10th, the foaming black and white pulp quality ratio is 1.0:0.1-0.1:Between 1.0.
In order to suppress the reaction of amino and NCO in free foaming forming process, density is obtained relatively low and heat-resisting
Property, heat endurance and anti-flammability is excellent and NCO polyimide foam with certain mechanical strength, the present invention passes through
The mode of existing two kinds of NCOs mutual grafting of polyimide foam preparation method is inhibited certainly to a certain extent
By the growing amount of polyureas in foamed forming process, while ensure that expansion ratio higher, there is provided a kind of low-density, high fire-retardance
Property the new method for preparing of NCO polyimide foam.NCO polyimide foam prepared by methods described is in half
Hole-closing structure, foam structure be uniform, with certain mechanical strength, while foam heat endurance, heat resistance and anti-flammability are basic
It is basically identical with pure polyimide foam.This method uses free foaming molding mode, material purity requirement and two-step method phase
Than substantially reduction, technological process significantly simplifies compared with two-step method, industrial mass production is thus susceptible to, while can be significantly
Degree reduces Polyimide foams price, further widens it in sophisticated technology field and the application model of common art
Enclose.
Compared with prior art, the present invention is due to using two kinds of traditional NCO polyimide foam preparation methods
The mode of mutual grafting, it is suppressed that amino and the generation of NCO in foamed material preparation process, reduces the life of polyureas
Cheng Liang, is improved the heat resistance of NCO polyimide foam, heat endurance, anti-flammability.It is different described in this method
Cyanic acid ester group polyimide foam preparation technology flow is simple, product high comprehensive performance, is conducive to industrialized production and extensively
Using.
Specific embodiment
The present invention is described in further detail by the following examples, scope involved in the present invention is not limited.Embodiment
In foam stabiliser include：Non-hydrolytic type water soluble polyether siloxanes (AK8805, DC193, L580)；Surfactant bag
Include：Non-ion fluorin carbon surface active agent (), polyoxyethylene nonionic surface live
Property agent (PEG-600, PEG-300, PEG-400, PEG-800, PEG-1000).Catalyst includes：Triethanolamine, triethylene two
Amine, stannous octoate, dibutyl tin laurate, Dabco33-LV；Foaming agent includes：Deionized water.
Embodiment 1
In 500ml there-necked flasks, add 200 grams of DMFs and 109 grams of pyromellitic acid dianhydrides and add
Magneton, connects reflux condensing tube and is passed through cooling water, is sufficiently stirred for being to slowly warm up to 90 DEG C under magnetic stirrer effect, treats equal benzene
Tetracarboxylic dianhydride is completely dissolved, and heating is stopped when solution is in clear state, with constant pressure funnel when temperature is down to 50 DEG C or so
To 32 grams of methyl alcohol are dropwise instilled in turbid liquid, rate of addition control is per minute at 1-5 milliliters, pyromellitic acid dianhydride is proceeded by ester
Change reaction, reaction to be esterified is carried out completely, solution is again after clear, and magnetic stirrer stops stirring, and above-mentioned solution is quiet
Put and be down to room temperature, be obtained and connect subdiaphanous transparent two acid diesters solution, lucifuge storage is stand-by.
7 grams of above-mentioned two acid diesters solution are weighed, 3 grams of foam stabilisers, 3 grams of polyoxyethylene surfactants, 0.2 are added
Gram fluorocarbon surfactant, 2 grams of catalyst compounded, 4 grams of deionized waters, obtain white material after being sufficiently stirred for.
In 100ml there-necked flasks, 36 grams of DMFs, 20 grams of pyromellitic acid dianhydrides, benzene more than 27 grams are added
Quito methylene polyisocyanates simultaneously adds magneton, is placed in oil bath pan, accesses nitrogen protection device, under magnetic stirrer effect
It is sufficiently stirred for being to slowly warm up to 50 DEG C, heats 2 hours, solution is changed into orange red clear state, obtains black material.Stop heating, it is fast
Be placed in for black material room temperature be cooled in ice-water bath by speed, then pours at once in white material, is quickly stirred with electric stirring oar, treats
Rapid pouring into mould makes its free foaming when mixture starts foaming and raising, and foam intermediate stands 3- under room temperature environment
After 5 minutes, it is transferred to and is previously heated to solidify 120 minutes in 260 DEG C of electric drying oven with forced convection, NCO polyamides is obtained sub-
Amine foam.Obtained Polyimide foams density is about 79 kilograms every cubic metre, in brown color, with certain machinery
Intensity, limited oxygen index value is up to 36%.
Embodiment 2
Weigh 21 grams of above-mentioned two acid diesters solution, add 3 grams of foam stabilisers, 3 grams of polyoxyethylene surfactants,
0.2 gram of fluorocarbon surfactant, 2 grams of catalyst compounded, 4 grams of deionized waters, obtain white material after being sufficiently stirred for.
In 100ml there-necked flasks, 28 grams of DMFs, 15 grams of pyromellitic acid dianhydrides, benzene more than 27 grams are added
Quito methylene polyisocyanates simultaneously adds magneton, is placed in oil bath pan, accesses nitrogen protection device, under magnetic stirrer effect
It is sufficiently stirred for being to slowly warm up to 50 DEG C, heats 2 hours, solution is changed into orange red clear state, obtains black material.Stop heating, it is fast
Be placed in for black material room temperature be cooled in ice-water bath by speed, then pours at once in white material, is quickly stirred with electric stirring oar, treats
Rapid pouring into mould makes its free foaming when mixture starts foaming and raising, and foam intermediate stands 3- under room temperature environment
After 5 minutes, it is transferred to and is previously heated to solidify 120 minutes in 260 DEG C of electric drying oven with forced convection, NCO polyamides is obtained sub-
Amine foam.Obtained Polyimide foams density is about 63 kilograms every cubic metre, in brown color, with certain machinery
Intensity, limited oxygen index value is up to 34%.
Embodiment 3
Weigh 35 grams of above-mentioned two acid diesters solution, add 3 grams of foam stabilisers, 3 grams of polyoxyethylene surfactants,
0.2 gram of fluorocarbon surfactant, 2 grams of catalyst compounded, 4 grams of deionized waters, obtain white material after being sufficiently stirred for.
In 100ml there-necked flasks, 20 grams of DMFs, 11 grams of pyromellitic acid dianhydrides, benzene more than 27 grams are added
Quito methylene polyisocyanates simultaneously adds magneton, is placed in oil bath pan, accesses nitrogen protection device, under magnetic stirrer effect
It is sufficiently stirred for being to slowly warm up to 50 DEG C, heats 2 hours, solution is changed into orange red clear state, obtains black material.Stop heating, it is fast
Be placed in for black material room temperature be cooled in ice-water bath by speed, then pours at once in white material, is quickly stirred with electric stirring oar, treats
Rapid pouring into mould makes its free foaming when mixture starts foaming and raising, and foam intermediate stands 3- under room temperature environment
After 5 minutes, it is transferred to and is previously heated to solidify 120 minutes in 260 DEG C of electric drying oven with forced convection, NCO polyamides is obtained sub-
Amine foam.Obtained Polyimide foams density is about 49 kilograms every cubic metre, in brown color, with certain machinery
Intensity, limited oxygen index value is up to 31%.
Embodiment 4
Weigh 50 grams of above-mentioned two acid diesters solution, add 3 grams of foam stabilisers, 3 grams of polyoxyethylene surfactants,
0.2 gram of fluorocarbon surfactant, 2 grams of catalyst compounded, 4 grams of deionized waters, obtain white material after being sufficiently stirred for.
In 100ml there-necked flasks, 12 grams of DMFs, 6.5 grams of pyromellitic acid dianhydrides, benzene more than 27 grams are added
Quito methylene polyisocyanates simultaneously adds magneton, is placed in oil bath pan, accesses nitrogen protection device, under magnetic stirrer effect
It is sufficiently stirred for being to slowly warm up to 50 DEG C, heats 2 hours, solution is changed into orange red clear state, obtains black material.Stop heating, it is fast
Be placed in for black material room temperature be cooled in ice-water bath by speed, then pours at once in white material, is quickly stirred with electric stirring oar, treats
Rapid pouring into mould makes its free foaming when mixture starts foaming and raising, and foam intermediate stands 3- under room temperature environment
After 5 minutes, it is transferred to and is previously heated to solidify 120 minutes in 260 DEG C of electric drying oven with forced convection, NCO polyamides is obtained sub-
Amine foam.Obtained Polyimide foams density is about 37 kilograms every cubic metre, in brown color, with certain machinery
Intensity, limited oxygen index value is up to 28%.
Claims (8)
1. a kind of preparation method of NCO polyimide foam, it is characterized in that：
(1) polynary fragrant acid anhydride heating for dissolving in polar solvent is reacted with fatty alcohol, obtains polynary fragrant acid anhydride derivative solution, is had
Body is：To polar solvent and polynary fragrant acid anhydride is sequentially added in container, stir and heat, treat that emulsion temp reaches 40-50 DEG C
When be added thereto to fatty alcohol and carry out esterification, the derivative solution of formation clear after reaction 2-3 hour；
(2) derivative solution and the foam stabiliser white material of compounding synthesis, specially：Under room temperature condition in derivative solution successively
The foaming that addition catalyst, foam stabiliser, surfactant and deionized water were uniformly mixed and obtained clear is white
Material；
(3) polynary fragrant acid anhydride is synthesized black material with isocyanates, specially：Successively by polar solvent, polynary under room temperature condition
Fragrant acid anhydride and isocyanates are added rapidly in container, access nitrogen protection device, container is placed in oil bath pan and is heated, and stirred
Mix, the black material that foams is obtained after polynary fragrant anhydride reactant is complete；
(4) the white material that will be foamed under room temperature condition of normal pressure is poured into the black material of foaming at once, rapid after stirring to pour into mould certainly
Foam intermediate is obtained by foaming；
(5) foam intermediate is obtained kind of a NCO polyimide foam by being heating and curing.
2. the preparation method of NCO polyimide foam according to claim 1, it is characterized in that the matter of each component
Measuring number is：Polynary fragrant acid anhydride is 120-200 parts, polar solvent is 100-200 parts, fatty alcohol is 5-20 parts, foam stabiliser
10-20 parts, surfactant 10-20 parts, catalyst 5-10 parts, deionized water be 10-20 parts, polyisocyanates 200-400 parts.
3. the preparation method of NCO polyimide foam according to claim 2, it is characterized in that the heating is solid
Change is specially：The demoulding after 3-5 minutes of foam intermediate room temperature, is transferred in 240-260 DEG C of electric drying oven with forced convection solid
Change 2-3 hours.
4. the preparation method of NCO polyimide foam according to claim 3, it is characterized in that the polynary virtue
Fragrant acid anhydride is：Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride, 3,3 ',
4,4 '-oxydiphthalic, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, the acid anhydride of mellitic acid three, three trimellitic anhydride -1,
The ester of 3,5- benzene three or 1,3,5- tri- oxygen-three (4- phthalic anhydrides) benzene.
5. the preparation method of NCO polyimide foam according to claim 4, it is characterized in that the polarity is molten
Agent is：1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO).
6. NCO polyimide foam according to claim 5 preparation method, it is characterized in that the catalysis
Agent is：Triethanolamine, triethylenediamine, stannous octoate, dibutyl tin laurate or Dabco33-LV；Foaming agent includes：
Deionized water.
7. the preparation method of NCO polyimide foam according to claim 6, it is characterized in that the oil bath pan
Constant heating-up temperature is 30-70 DEG C.
8. the preparation method of NCO polyimide foam according to claim 7, it is characterized in that the foaming is black
White pulp quality ratio is 1.0:0.1-0.1:Between 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510193907.9A CN104829835B (en) | 2015-04-22 | 2015-04-22 | Preparation method of isocyanate-based polyimide foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510193907.9A CN104829835B (en) | 2015-04-22 | 2015-04-22 | Preparation method of isocyanate-based polyimide foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104829835A CN104829835A (en) | 2015-08-12 |
| CN104829835B true CN104829835B (en) | 2017-05-24 |
Family
ID=53808057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510193907.9A Active CN104829835B (en) | 2015-04-22 | 2015-04-22 | Preparation method of isocyanate-based polyimide foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104829835B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280451A (en) * | 2016-09-14 | 2017-01-04 | 郑州峰泰纳米材料有限公司 | The preparation method of hard polyimide foaming |
| CN106589373B (en) * | 2016-12-09 | 2019-03-29 | 江苏五信新材料科技股份有限公司 | A kind of super-hydrophobic polyimide foam and preparation method thereof |
| CN106751826B (en) * | 2017-01-17 | 2019-02-01 | 自贡中天胜新材料科技有限公司 | A kind of activeness and quietness self-curing hard polyimide foaming and preparation method thereof |
| CN111217999B (en) * | 2020-02-20 | 2022-07-26 | 哈尔滨工程大学 | Environment-friendly preparation method of flexible polyimide heat insulation foam and product |
| CN113185747B (en) * | 2021-05-11 | 2022-07-05 | 贵州航天天马机电科技有限公司 | Preparation method of hard polyimide foam material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497255A (en) * | 2015-01-13 | 2015-04-08 | 哈尔滨工程大学 | One-step high-flame-retardance low-density polyimide foam preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4552104B2 (en) * | 2003-04-25 | 2010-09-29 | Ｄｉｃ株式会社 | Thermosetting polyimide resin composition, method for producing polyimide resin, and polyimide resin |
-
2015
- 2015-04-22 CN CN201510193907.9A patent/CN104829835B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497255A (en) * | 2015-01-13 | 2015-04-08 | 哈尔滨工程大学 | One-step high-flame-retardance low-density polyimide foam preparation method |
Non-Patent Citations (3)
| Title |
|---|
| Effects of hydrotalcites and tris (1-chloro-2-propyl) phosphate on thermal stability, cellular structure and fire resistance of isocyanate-based polyimide foams;Gaohui Sun, et al.;《Polymer Degradation and Stability》;20150204;第115卷;第1-15页 * |
| Enhanced polyimide proportion effects on fire behavior of isocyanate-based polyimide foams by refilled aromatic dianhydride method;Gaohui Sun, et al.;《Polymer Degradation and Stability》;20140820;第110卷;第2-3页第2.2节 * |
| 超轻、阻燃型异氰酸酯基聚酰亚胺泡沫塑料的新型制备方法与性能研究;孙高辉 等;《2013年全国高分子学术论文报告会论文摘要集——主题M：阻燃高分子》;20131016;第910页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104829835A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104829835B (en) | Preparation method of isocyanate-based polyimide foam | |
| CN101812232B (en) | Polyimide foam and preparation method thereof | |
| CN101402743B (en) | Polyimide foam and method of producing the same | |
| CN102093714B (en) | Light flexible polymide foam material and preparation method thereof | |
| CN102134395B (en) | Modified light flexible polyimide foam material and preparation method thereof | |
| CN101407594B (en) | Modified polyimides foam and preparation thereof | |
| CN107540839B (en) | Light sound-absorbing heat-insulating polyimide foam material and preparation method thereof | |
| CN101402795B (en) | Novel fire resistant polyimide foam and method of producing the same | |
| CN104910380A (en) | Preparation method of honeycomb-reinforced polyimide foam composite material | |
| CN106589373B (en) | A kind of super-hydrophobic polyimide foam and preparation method thereof | |
| CN102134396A (en) | Light flexible polyimide foam material and preparation method thereof | |
| CN105153422B (en) | A kind of Polyimide foams and preparation method thereof | |
| CN102964834B (en) | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof | |
| CN102618034B (en) | Method for preparing polyether amine modified isocyanate group polyimide foam | |
| CN103897395A (en) | Preparation method of hydrotalcite and polyimide composite foam material | |
| CN107540841B (en) | Preparation method of hard closed-cell polyimide foam | |
| CN103030763B (en) | Polyimide modified polyisocyanurate foam and preparation method thereof | |
| CN108715636A (en) | A kind of halogen-free flameproof Polyimide foams and preparation method thereof | |
| CN111592649A (en) | Low-thermal-conductivity polyimide foam material and preparation method thereof | |
| CN104559201A (en) | Method for preparing polyimide-organic silicon composite foam material | |
| CN104497255A (en) | One-step high-flame-retardance low-density polyimide foam preparation method | |
| CN107353385A (en) | The preparation method of High-temperature-respolyurethane polyurethane foam material | |
| CN106280451A (en) | The preparation method of hard polyimide foaming | |
| CN105175724A (en) | Preparation method of ultralow-density polyimide porous material by one-step process | |
| CN105315464B (en) | Prepare the method with regular three-dimensional dimension polyimide foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |