CN101735457A - Production method of soft polyimide foam - Google Patents
Production method of soft polyimide foam Download PDFInfo
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- CN101735457A CN101735457A CN201010034119A CN201010034119A CN101735457A CN 101735457 A CN101735457 A CN 101735457A CN 201010034119 A CN201010034119 A CN 201010034119A CN 201010034119 A CN201010034119 A CN 201010034119A CN 101735457 A CN101735457 A CN 101735457A
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Abstract
The invention provides a production method of soft polyimide foam, comprising the following steps: adding one or more than two kinds of aromatic dianhydride in polar solvent to be totally dissolved; then, adding aromatic diamine to generate amic acid; after reaction, adding two or more than two kinds of foaming agents, and adding one or more than two catalysts and surfactants; at room temperature, mixing the mixture with water and one or more than two kinds of aromatic isocyanate, and foaming; and finally, ripening generated foam in a microwave oven and a high temperature furnace. The polyimide foam obtained by the invention is soft, has elasticity and has favorable sound absorption performance and fire resistance; and the foam density is 4.0-8.0 kg/m3; foam stops firing when foam is far away from fire, so that the amount of emitted smog is small, and no drippage objects exist. Meanwhile, the polyimide foam of the invention has favorable thermal insulation property. The polyimide foam of the invention can be suitable for the fields of aerospace, military ships and the like.
Description
Technical field
The present invention relates to a kind of production method of polyimide foam, specifically, relate to a kind of production method of soft polyimide foam.
Background technology
The material that is used for heat insulating at present mainly is polyurethane foam and phenol formaldehyde foam.But polyurethane foam is not fire-retardant, and burning the time produces a large amount of droppings and a large amount of smog, and smoke density reaches more than 80%; Phenol formaldehyde foam has good flame retardancy, but this foam does not have intensity, easily efflorescence, and density is too high.And polyimide foam when burning drippage not, its smoke density has only 8%.
Polyimide is the fabulous polymkeric substance of a kind of thermotolerance, has good mechanical and electrical property and radiation hardness and corrosion resistance nature, is widely used in fields such as aerospace, military affairs, electronics.The polyimide material of foamy structure has not only kept the heatproof of unmodified resin excellence, performance such as fire-retardant, also have over-all propertieies such as outstanding saturating wave property and light weight, flexible resilience are good, easy to use, therefore extremely important purposes is arranged on military equipment.
Polyimide foam is divided into hard polyimide and soft polyimide, adopts benzophenone tetracarboxylic dianhydride, diamine and whipping agent to form through foaming such as the hard polyimide more.And some soft thermoplastic polyimide foams uses thermoplastic polyimide powder to add whipping agent to form the homogeneity of abscess and the less stable of technology in the high temperature foaming; The foamy resistance to elevated temperatures is also relatively poor.And the polyimide foam that has directly uses the esterification solution and the isocyanate reaction slaking of two acid anhydrides to obtain, and the foamy mechanical property is relatively poor.
Such as, in US 5298531 and 5122546, in 5077318, all be to adopt to generate performed polymer earlier, promptly earlier one or both pairs acid anhydride is dissolved in the polar solvent, small molecular alcohols such as adding methyl alcohol make its esterification or half esterization, in this solution, add aromatic series or aliphatie diamine again, remove the small molecules powdered in the first solution after question response is complete, make it emit micromolecular method foaming such as water and methyl alcohol by high temperature in this powder later on, main drawback is that the drying of performed polymer is very complicated, and the density of foams is too high, can not the lower foam of production density.
The disclosed a kind of novel fire resistant polyimide foam of CN101402795A, it also is by with two acid anhydride esterifications, and the method that adds active diamine in solution is produced the powder performed polymer, produces polyimide foam by two-step approach, and this foam is rigid foam, and density is 100-500kg/m
3, be not suitable for low-density foam production.
US7541388 is disclosed to be a kind of synthetic method of novel fire resistant polyimide foam, it also is by with two acid anhydride esterifications, make it at foaming at normal temp rapid mixing of this esterification solution with the mixture of isocyanic ester, slaking in microwave oven, thereby obtain the lower polyimide foam of density, it presses limit intensity (50%) is 2-3KPa.
Summary of the invention
The purpose of this invention is to provide a kind of production method of soft polyimide foam, it is low that this method obtains polyimide foam density, and the flame retardant properties excellence has the sound absorption heat insulation function simultaneously.
Another object of the present invention provides a kind of soft polyimide foam of being made by this method, and its foam density is low, and the flame retardant properties excellence has the sound absorption heat insulation function simultaneously.
In order to realize the object of the invention, the invention provides a kind of production method of soft polyimide foam, it comprises the steps:
1) in polar solvent, adds the two acid anhydrides of one or both fragrants it is dissolved fully, add aromatic diamine then, generate amido acid;
2) the reaction back adds two or more whipping agent, and adds one or more catalyzer, and tensio-active agent;
3) and then at room temperature mix, then foaming with water and one or more aromatic isocyanates;
4) at last the foam that generates is made its slaking in microwave oven and High Temperature Furnaces Heating Apparatus.
Wherein, the two acid anhydrides of fragrant of the present invention can be pyromellitic acid dianhydride (PMDA), two phthalic anhydride ethers (BDTA).
Described polar solvent can be N, one or both in dinethylformamide (DMF) or the N,N-DIMETHYLACETAMIDE (DMAC).
Solvent temperature in the step 1) is controlled at 100-120 ℃, is preferably 100 ℃.
After adding aromatic diamine, solution temperature is controlled to 110-120 ℃, is advisable with 120 ℃, and the two acid anhydrides and the sufficient reacting of diamines are carried out, and temperature is reduced to 50-60 ℃ behind the generation amido acid.
Being used for the aromatic diamine of synthesizing amide acid can be 1,1 ' diaminodiphenyl oxide, one or more in 1,4 diaminodiphenyl oxide or the methylene dianiline (MDA).
Described whipping agent is one or more in methyl alcohol, ethanol or the ethylene glycol ethyl ether.
Described catalyzer is Niax A-1, the A-33 of Mai Tu chemical company, one or more among the BL17 of gas companies or the K-19 of goldschmidt chemical corporation.
In order to obtain uniform foam structure, in mixed solution, add tensio-active agent.Described tensio-active agent is B8 404, the L6900 of Mai Tu company, the DC193 of gas companies or the AK 8801 of dolantin generation wound company of goldschmidt chemical corporation.
Described isocyanic ester is the methylene radical Xylene Diisocyanate (MDI) of polyphenyl polyisocyanate (PAP1), Beyer Co., Ltd of BASF AG or one or more the mixture in the tolylene diisocyanate (TDI).
All raw materials all carry out chemosynthesis reaction according to a certain percentage among the present invention.Such as, be reference with the two acid anhydrides of 100 gram fragrants, the consumption of isocyanic ester restrains at 100-150, and the consumption of polar solvent is the 250-300 gram; The consumption of aromatic diamine is between the 2-15 gram, and catalyst consumption is between the 0.03-0.1 gram, and the consumption of tensio-active agent is between the 10-20 gram, and the consumption of whipping agent is between the 6-20 gram, and the consumption of water is between the 10-15 gram.
In order to mix, used the high speed agitator of rotating speed as 2500-4000rpm, the time of stirring is 4-15 second; The mixture that stirs is poured into rapidly in an opening or the mould of remaining silent, be allowed to condition at free foaming in the room temperature, in this process, this mixture expands rapidly, solidifies, and produces a kind of foam performed polymer of small molecular weight.
The foaming of this performed polymer is carried out at normal temperatures, and generally this foam is slaking 10-15 minute at room temperature, treats to move in the microwave oven after not touching with one's hand in its surface to make its complete slaking.The power of microwave oven is between 800-1200kw, and the time of slaking is 10-15 minute; The slaking from the inside to the outside in microwave oven of this foam performed polymer, the foam after the microwave oven slaking moves in the high temperature oven again, makes foam slaking from outside to inside.The time of this performed polymer slaking in high temperature oven is 10-15 minute, and the temperature of high temperature oven is 200-250 ℃.
The production method of polyimide of the present invention is compared with US7541388, following difference is arranged: 1) the present invention elder generation synthesizing amide acid in the first step, and US7541388 directly carries out esterification, the present invention is by first synthesizing amide acid in solution, final foamy molecular weight is improved, thereby has improved the physical strength of foam article; 2) the 3rd the step foamable reaction in water as an independent component and pre-gathering solutions and isocyanic ester foamable reaction; In US7541388 water directly added in the solution after the esterification of two acid anhydrides, water has been participated in the esterification of two acid anhydrides directly as esterifying agent.Among the present invention,, be easier to the density and the foam structure of control foam, make entire reaction have controllability because moisture content adds separately.The foam density scope that obtains among the US7541388 is at 4-5kg/m
3Between, pressing limit intensity (50%) is 2-3KPa; And the polyimide foam that the present invention obtains presses limit intensity (50%) can reach 3-5KPa, and tensile strength reaches 40-60KPa.Wherein the testing method of related froth product is ASTM D 3574-95.
Therefore, the present invention obtains the polyimide foam softness, and is flexible, and density is at 4.0-8.0kg/m
3, have sound absorbing capabilities preferably, flame retardant properties.And foam stops up from fire and puts out, and the amount of smoke of distributing is few, no dropping.Polyimide foam of the present invention also has good heat-insulating property simultaneously.Polyimide foam of the present invention is applicable to aerospace, fields such as Military Ship.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In one 500 milliliters there-necked flask, add the DMF solvent of 200 grams and the PMDA of 84 grams, slowly be warming up to 100 ℃, stirring is dissolved PMDA fully, solution is the yellow transparent shape, in this solution, add 3 grams 1,1 ' diaminodiphenyl oxide ODA, and temperature risen to 120 ℃, solution becomes the viscous liquid of rust red.
This solution is cooled to 50 ℃, is docile and obedient preface and slowly adds 12 gram methyl alcohol, 2 gram ethylene glycol ethyl ethers, the A-10.03 gram, the A-330.03 gram, the K-190.01 gram also adds 12 gram B8404 simultaneously, mixes, and reduces to 25 ℃.
Get above solution 50 grams, water 2.5 grams, the PAPI22 gram mixes rapidly in high speed agitator and stirs, speed is 3000rpm, churning time 10 seconds is poured into rapidly in the paper matrix after the stirring, allows its free foaming, after 15 minutes, treat that its surface dry and comfortablely do not touch with one's hand, this performed polymer foam moved in microwave oven that slaking is 10 minutes when power 1000W.Slaking 10 minutes in 200 ℃ High Temperature Furnaces Heating Apparatus again after from microwave oven, taking out.
Gained foam article softness, even structure, abscess exquisiteness.Foam density is 4.2kg/m
3Press limit intensity (50%) can reach 3.2KPa, tensile strength reaches 40KPa.
Embodiment 2
In one 500 milliliters there-necked flask, add the DMF solvent of 200 grams and the PMDA of 84 grams, slowly be warming up to 100 ℃, stirring is dissolved PMDA fully, solution is the yellow transparent shape, in this solution, add 6 grams, 1,1 ' diaminodiphenyl oxide ODA, 6 gram methylene dianiline (MDA) MDA, and temperature risen to 120 ℃, solution becomes the viscous liquid of rust red.
This solution is cooled to 50 ℃, is docile and obedient preface and slowly adds 6 gram methyl alcohol, 1 gram ethylene glycol ethyl ether, the A-10.03 gram, the A-330.03 gram, the K-190.01 gram also adds 12 gram B8404 simultaneously, mixes, and reduces to 25 ℃.
Get above solution 50 grams, 2.2 gram water, PAPI 15 grams, MDI 9 restrain to mix rapidly in high speed agitator and stir, speed is 2500rpm, churning time 7 seconds is poured into rapidly in the paper matrix after the stirring, allows its free foaming, after general 10 minutes, treat that its surface dry and comfortablely do not touch with one's hand, this performed polymer foam moved in microwave oven that slaking is 12 minutes when power 1200W.Slaking 10 minutes in 220 ℃ High Temperature Furnaces Heating Apparatus again after from microwave oven, taking out.
Gained foam article softness, even structure, abscess exquisiteness.Foam density is 7.0kg/m
3Press limit intensity (50%) can reach 4.8KPa, tensile strength reaches 60KPa.
Embodiment 3
In one 500 milliliters there-necked flask, add the DMF solvent of 200 grams and the PMDA and the 15 gram BDTA of 75 grams, slowly be warming up to 100 ℃, stirring is dissolved PMDA and BDTA fully, solution is the yellow transparent shape, in this solution, add 6 grams 1,1 ' diaminodiphenyl oxide ODA also rises to 120 ℃ with temperature, and solution becomes the viscous liquid of rust red.
This solution is cooled to 50 ℃, is docile and obedient preface and slowly adds 8 gram methyl alcohol, 1 gram ethylene glycol ethyl ether, the A-10.03 gram, the A-330.03 gram, the K-190.01 gram also adds 12 gram B8404 simultaneously, mixes, and reduces to 25 ℃.
Get above solution 50 grams, water 2.6 grams, PAPI 27 grams stir rapidly in high speed agitator, speed is 2500rpm, churning time 10 seconds is poured into rapidly in the paper matrix after the stirring, allows its free foaming, after general 12 minutes, treat that its surface dry and comfortablely do not touch with one's hand, this performed polymer foam moved in microwave oven that slaking is 15 minutes when power 1000W.Slaking 10 minutes in 250 ℃ High Temperature Furnaces Heating Apparatus again after from microwave oven, taking out.
Gained foam article softness, even structure, abscess exquisiteness.Foam density is 6.0kg/m
3Press limit intensity (50%) can reach 4.4KPa, tensile strength reaches 50KPa.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a production method of soft polyimide foam is characterized in that it comprises the steps:
1) in polar solvent, adds the two acid anhydrides of one or both fragrants it is dissolved fully, add aromatic diamine then, generate amido acid;
2) the reaction back adds two or more whipping agent, and adds one or more catalyzer, and tensio-active agent;
3) and then at room temperature mix, then foaming with water and one or more aromatic isocyanates;
4) at last the foam that generates is made its slaking in microwave oven and High Temperature Furnaces Heating Apparatus.
2. method according to claim 1 is characterized in that, the two acid anhydrides of described fragrant are pyromellitic acid dianhydride, two phthalic anhydride ethers.
3. method according to claim 1 and 2 is characterized in that, described polar solvent is one or both among DMF or the DMAC.
4. according to any described method of claim 1-3, it is characterized in that described aromatic diamine is 1,1 ' diaminodiphenyl oxide, one or more in 1,4 diaminodiphenyl oxide or the methylene dianiline (MDA).
5. according to any described method of claim 1-4, it is characterized in that described whipping agent is one or more in methyl alcohol, ethanol or the ethylene glycol ethyl ether.
6. according to any described method of claim 1-5, it is characterized in that described catalyzer is Niax A-1, A-33, BL 17 or K-19.
7. according to any described method of claim 1-6, it is characterized in that described isocyanic ester is one or more the mixture in polyphenyl polyisocyanate, methylene radical Xylene Diisocyanate or the tolylene diisocyanate.
8. according to any described method of claim 1-7, it is characterized in that, mix in the step 3) to adopt and under the high speed agitator of 2500-4000rpm, stir 4-15 second.
9. according to any described method of claim 1-8, it is characterized in that the power of microwave oven is between 800-1200kw, the time of slaking is 10-15 minute; Temperature is 200-250 ℃ in the high temperature oven, and the time is 10-15 minute.
10. by any soft polyimide foam that described method is produced of claim 1-9, it is characterized in that described soft polyimide foam density is at 4.0-8.0kg/m
3
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| CN2010100341192A CN101735457B (en) | 2010-01-15 | 2010-01-15 | Production method of soft polyimide foam |
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| CN2010100341192A CN101735457B (en) | 2010-01-15 | 2010-01-15 | Production method of soft polyimide foam |
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| CN101735457B CN101735457B (en) | 2012-06-27 |
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| CN103232599A (en) * | 2013-05-10 | 2013-08-07 | 中国科学院长春应用化学研究所 | Polyimide foam and preparation method thereof |
| CN104017215A (en) * | 2013-02-28 | 2014-09-03 | 比亚迪股份有限公司 | Polyimide resin, preparation method thereof and polyimide foam |
| CN105924649A (en) * | 2016-05-19 | 2016-09-07 | 航天材料及工艺研究所 | Polyimide foam material and preparation method thereof |
| CN106380600A (en) * | 2016-09-14 | 2017-02-08 | 郑州峰泰纳米材料有限公司 | Preparation method for flexible polyimide foam |
| CN107540839A (en) * | 2016-06-27 | 2018-01-05 | 上海康达化工新材料股份有限公司 | A kind of heat-insulated Polyimide foams of Lightweight acoustical and preparation method thereof |
| CN112694615A (en) * | 2020-12-30 | 2021-04-23 | 青岛海洋新材料科技有限公司 | Polyimide soft low-density sound absorption foam and preparation method thereof |
| CN115322568A (en) * | 2022-08-31 | 2022-11-11 | 常州福隆科技新材料有限公司 | Polyimide foam material based on fluorine-containing polyamic acid precursor and preparation method thereof |
Family Cites Families (5)
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| US6956066B2 (en) * | 2003-02-11 | 2005-10-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyimide foams |
| CN101353408B (en) * | 2008-09-09 | 2010-09-08 | 北京市射线应用研究中心 | Polyurethane acid imide foam material and preparation thereof |
| CN101402743B (en) * | 2008-11-25 | 2011-02-02 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN101407594B (en) * | 2008-11-25 | 2012-03-21 | 北京市射线应用研究中心 | Modified polyimides foam and preparation thereof |
| CN101463120B (en) * | 2009-01-13 | 2010-10-06 | 北京市射线应用研究中心 | Method for preparing polyurethane acid imide foam material |
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2010
- 2010-01-15 CN CN2010100341192A patent/CN101735457B/en active Active
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| CN104017215A (en) * | 2013-02-28 | 2014-09-03 | 比亚迪股份有限公司 | Polyimide resin, preparation method thereof and polyimide foam |
| CN104017215B (en) * | 2013-02-28 | 2016-09-07 | 比亚迪股份有限公司 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
| CN103232599A (en) * | 2013-05-10 | 2013-08-07 | 中国科学院长春应用化学研究所 | Polyimide foam and preparation method thereof |
| CN105924649A (en) * | 2016-05-19 | 2016-09-07 | 航天材料及工艺研究所 | Polyimide foam material and preparation method thereof |
| CN105924649B (en) * | 2016-05-19 | 2019-06-18 | 航天材料及工艺研究所 | A kind of Polyimide foams and preparation method thereof |
| CN107540839A (en) * | 2016-06-27 | 2018-01-05 | 上海康达化工新材料股份有限公司 | A kind of heat-insulated Polyimide foams of Lightweight acoustical and preparation method thereof |
| CN106380600A (en) * | 2016-09-14 | 2017-02-08 | 郑州峰泰纳米材料有限公司 | Preparation method for flexible polyimide foam |
| CN112694615A (en) * | 2020-12-30 | 2021-04-23 | 青岛海洋新材料科技有限公司 | Polyimide soft low-density sound absorption foam and preparation method thereof |
| CN115322568A (en) * | 2022-08-31 | 2022-11-11 | 常州福隆科技新材料有限公司 | Polyimide foam material based on fluorine-containing polyamic acid precursor and preparation method thereof |
| CN115322568B (en) * | 2022-08-31 | 2023-10-13 | 常州福隆科技新材料有限公司 | Polyimide foam material based on fluorine-containing polyamic acid precursor and preparation method thereof |
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