CN105315464A - Method for preparing polyimide foam with structured three-dimensional sizes - Google Patents
Method for preparing polyimide foam with structured three-dimensional sizes Download PDFInfo
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- CN105315464A CN105315464A CN201510789825.0A CN201510789825A CN105315464A CN 105315464 A CN105315464 A CN 105315464A CN 201510789825 A CN201510789825 A CN 201510789825A CN 105315464 A CN105315464 A CN 105315464A
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- polyimide foam
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Abstract
The invention provides a method for preparing polyimide foam with structured three-dimensional sizes. The method comprises the following steps: firstly, reacting multiple aromatic acid anhydride and fatty alcohol in a polar solvent to prepare a carboxylic ester solution; then, compounding the carboxylic ester solution with a catalyst, a surfactant and a foaming agent to obtain a foaming white material; finally, pouring isocyanate into the foaming white material, quickly mixing, and when the materials are uniformly mixed, quickly pouring the mixed slurry into a steel die for closed foaming, so as to obtain a polyimide foam intermediate; putting the polyimide foam intermediate together with the die into a high-temperature drying oven for curing, so as to finally obtain the high-strength polyimide foam with structured three-dimensional sizes. The prepared polyimide foam is relatively high in heat resistance, fire resistance and compression strength, and can be directly used as a structural material; the compression strength of the material can be directly adjusted through the ratio of foaming slurry mass to the steel die volume; the technology is simple, and the product price is low; the prepared polyimide foam has structured three-dimensional sizes.
Description
Technical field
That the present invention relates to is a kind of preparation method of High Strength Polyimide foam materials, particularly a kind ofly prepares the method with regular three-dimensional dimension High Strength Polyimide foam.
Background technology
Polyimide foam is a kind of is fill phase with gas, polyimide is the porous material of matrix, gather imide high-low temperature resistant, resistance to irradiation, the fire-retardant and premium properties such as vesicular structure lightweight, heat insulating, sound absorption vibration damping, be therefore widely used in the leading-edge fields such as aerospace, boats and ships, bullet train.
Polyimide foam can be divided into hard, semi-rigid and soft polyimide foam according to compressive strength.Current most typical hard polyimide foaming surely belongs to Polymethacrylimide (PMI) foam, is widely used in the support in the fields such as aerospace, withstand voltage, structured material; Soft polyimide foam mainly comprises common single stage method and two-step approach polyimide foam, is mainly used as flexible lining materials'use, still can not be used alone as structural support material and use.Although PMI foam shows obvious mechanical property advantage compared with single stage method and two-step approach polyimide foam, but because PMI foam belongs to side-chain polyimide foam, virtue in resinous molecular structure, heterocycle content is relatively low, therefore can not mention in the same breath with backbone chain type polyimide foams such as single stage method and two-step approach polyimide foams at the aspect of performance such as fire-retardant, high-low temperature resistant, resistance to irradiation, there is larger use safety hidden danger.Although disclose the method improving PMI foam safety in utilization in the patent documentations such as CN103524968A, CN103554354A, CN1610719A, but related performance indicators does not still reach the level of backbone chain type polyimide foam, and the method announced more or less all can cause the decline of material mechanical performance.Therefore for preparing the High Strength Polyimide foam with excellent safety in utilization, the preparation that sight is targeted to high strength backbone chain type Polyimide foams by numerous scientists comes up, to expect the Application Areas widening polyimide foam further.
For preparing high strength backbone chain type polyimide foam, in succession report the method such as microwave, microballoon, mold pressing of relying on two-step approach polyimide foam preparation technology in the patent documentations such as US5077318, US6180746, CN103012793A, also report the compression molding of relying on single stage method polyimide foam preparation technology in the patent document such as CN102127225A simultaneously.Compared with two-step approach preparation technology, one-step preparation process has the advantages such as preparation technology is simple, material cost is cheap, with short production cycle, therefore advantageously in the realization of suitability for industrialized production.
The single stage method High Strength Polyimide foam reported in the patent documents such as CN102127225A is all first pass through mould pressurizing (1-20MPa) substantially, and then the mode of carrying out microwave radiation sizing obtains, the requirement of preparation process to special industry equipment is higher, operating process is simultaneously comparatively dangerous, is therefore not suitable for scale operation.
Summary of the invention
The object of the present invention is to provide that one can obtain thermotolerance, flame retardant resistance is higher, compressive strength is comparatively large, and the preparation with the polyimide foam of regular three-dimensional dimension has the method for regular three-dimensional dimension polyimide foam.
The object of the present invention is achieved like this:
By massfraction be polynary fragrant acid anhydride 150-400 part, polar solvent 100-200 part, fatty alcohol 5-10 part, suds-stabilizing agent 10-20 part, tensio-active agent 10-20 part, catalyzer 5-10 part, deionized water be that 10-20 part and polyisocyanates 300-600 part are prepared in accordance with the following steps
(1) polynary fragrant acid anhydride heating for dissolving and fatty alcohol in polar solvent reacts, and obtains polynary fragrant acid anhydride derivative carboxylicesters solution, specifically comprises:
Polar solvent and the polynary fragrant acid anhydride of 40-160 part is added successively in container, abundant stirring is also heated, when emulsion temp reaches 40-60 DEG C, add fatty alcohol wherein carry out esterification, react the carboxylicesters solution forming clear after 2-3 hour, leave standstill that to be cooled to room temperature stand-by;
(2) expect preparation in vain, specifically comprise:
In carboxylicesters solution, add the polynary fragrant acid anhydride of surplus, catalyzer, tensio-active agent and deionized water under room temperature condition successively, obtain white slip after being uniformly mixed for the white material of foaming;
(3) under room temperature condition of normal pressure, polyisocyanates is added in the white material of foaming and stir, form foaming slip, subsequently foaming slip to be poured in mould and tumble in top cover and form enclosed system, after 2-3 minute, end of processing to be foamed puts into 180-240 DEG C of high temperature oven, hot setting 2-3 hour by filling frothy closed mold;
(4) after having solidified, mould is naturally cooled to room temperature.
The present invention can also comprise:
1, described polynary fragrant acid anhydride is pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-oxydiphthalic (ODPA), 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, mellitic acid three acid anhydride, three trimellitic acid 1,2-anhydride-1,3,5-benzene three esters or 1,3,5-tri-oxygen-three (4-phthalic anhydride) benzene.
2, described intensive polar solvent is DMF (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO) (DMSO).
3, described fatty alcohol comprises for methyl alcohol or ethanol.
4, described tensio-active agent is non-hydrolytic type water soluble polyether siloxanes (AK8805, DC193, L580), polyoxyethylene nonionic tensio-active agent (PEG-600, PEG-300, PEG-400, PEG-800, PEG-1000).
5, described catalyzer is trolamine, triethylenediamine, stannous octoate, dibutyl tin laurate or Dabco33-LV; Whipping agent comprises: deionized water.
6, described polyisocyanates is diphenylmethanediisocyanate, tolylene diisocyanate, polyphenyl polymethylene polyisocyanates, hexamethylene diisocyanate or isophorone diisocyanate.
7, in described carboxylicesters solution preparation process, polynary fragrant acid anhydride consumption is 40-160 part, and in white material process for preparation, polynary fragrant acid anhydride powder consumption is 110-240 part.
8, by changing foaming slip total mass M (g) and encloses container cavity volume V (cm
3) ratio, control the density (ρ) of polyimide foam and compressive strength (σ
m), M/V in-scope is 0.09-0.18g/cm
3.
Compared with current techniques, the present invention relies on the single stage method technology of preparing of polyimide foam, by method controlled material density and the mechanical property of closed mold restraint of liberty foaming degree, the high strength backbone chain type Polyimide foams with excellent safety in utilization can be prepared quickly and safely.Meanwhile, by the foam materials prepared by present method, there is regular three-dimensional dimension, eliminate and follow-uply cut treating processes, can according to the actual requirements directly designing mould size produce material requested.This preparation method preparation technology is simple, material cost is cheap, processing safety and controllability is high, product price is lower, just obtained the High Strength Polyimide foam with regular size by simple technology, effectively improve the preparation technology of current high strength backbone chain type Polyimide foams.Operational path of the present invention is simple, and production security is higher, obtained material excellent combination property, is conducive to suitability for industrialized production and the widespread use of high strength backbone chain type Polyimide foams.
Embodiment
The method that preparation of the present invention has regular three-dimensional dimension High Strength Polyimide foam mainly comprises following content:
(1) instrument equipment comprises: there-necked flask, mechanical stirring oar, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel, steel mould and electric drying oven with forced convection; Described chemical feedstocks comprises polynary fragrant acid anhydride, polar solvent, fatty alcohol, tensio-active agent, catalyzer, deionized water and isocyanic ester, described material chemical constitution by massfraction is: polynary fragrant acid anhydride 150-400 part, polar solvent 100-200 part, fatty alcohol 5-10 part, suds-stabilizing agent 10-20 part, tensio-active agent 10-20 part, catalyzer 5-10 part, deionized water is 10-20 part, polyisocyanates 300-600 part; Preparation process used is:
(1) polynary fragrant acid anhydride heating for dissolving and fatty alcohol in polar solvent reacts, and obtains polynary fragrant acid anhydride derivative carboxylicesters solution:
Polar solvent and polynary fragrant acid anhydride is added successively according to formula in there-necked flask, abundant stirring is also placed in oil bath pan and heats, when emulsion temp reaches 40-60 DEG C, add fatty alcohol wherein carry out esterification, react the carboxylicesters solution forming clear after 2-3 hour, leave standstill that to be cooled to room temperature stand-by;
(2) preparation is expected in vain:
Take quantitative carboxylicesters solution under room temperature condition, add polynary fragrant acid anhydride powder, catalyzer, tensio-active agent and deionized water successively by formula, after being uniformly mixed with glass stick, obtain white slip, be defined as the white material of foaming;
(3) adding the polyisocyanates taken by filling a prescription in white material rapid stirring under room temperature condition of normal pressure even, forming foaming slip.Poured into rapidly in steel mould by foaming slip subsequently, mould is tumbled in fast top cover and form airtight steel system, after 2-3 minute, end of processing to be foamed puts into 180-240 DEG C of high temperature oven, hot setting 2-3 hour by filling frothy airtight steel mould;
(4) after having solidified, mould is naturally cooled to room temperature, open mould and take out foam materials.
By the following examples the present invention is described in further detail, and unrestricted scope involved in the present invention.
Embodiment 1
In 250ml there-necked flask, add 110 grams of DMFs and 45 gram 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) adds magneton, connect reflux condensing tube and pass into water coolant, under magnetic stirrer effect, abundant stirring is slowly warming up to 55 DEG C.In turbid liquid, dropwise instill 6 grams of methyl alcohol with constant pressure funnel, rate of addition controls at 1-5 milliliter per minute, makes BTDA start to carry out esterification.Reaction to be esterified is carried out completely, and solution is again after clear, and magnetic stirrer stops stirring.Above-mentioned solution left standstill is down to room temperature, obtains and connect subdiaphanous transparent carboxylates's solution, lucifuge stores stand-by.
According to carboxylicesters solution: polynary fragrant acid anhydride powder: suds-stabilizing agent: tensio-active agent: catalyst compounded: water is the white material of proportions foaming of 161:180:12:12:6:12, the white material of foaming takes with polyphenyl polymethylene polyisocyanates according to the mass ratio of 1:1, mixes, stir 15s with mechanical stirring oar, obtain the slip that foams.Subsequently according to foaming pulp quality and mold cavity volume 0.09g/cm
3proportionlity take rapidly foaming slip 45 grams, evenly pouring cavity volume into is 500cm
3and be lined with in the steel mould of polyethylene plastic film, tumble in top cover fast and form airtight steel system, after 3 minutes, steel enclosed system is put into 180 DEG C of baking oven hot settings 2 hours.After having solidified, steel enclosed system is naturally cooled to room temperature, after die sinking, obtain regular three-dimensional dimension foams.
Test foam correlated performance and proterties as follows:
Density: 43.85 kilograms per cubic meter
Longitudinal compressive strength: 251kPa
Horizontal compression intensity: 244kPa
Limiting oxygen index(LOI): 29%.
Embodiment 2
Have the High Strength Polyimide foam of regular three-dimensional dimension by the preparation of formula described in embodiment 1, foaming slip total mass and mold cavity volume ratio are 0.12g/cm
3.
Test foam correlated performance and proterties as follows:
Density: 54.66 kilograms per cubic meter
Longitudinal compressive strength: 400kPa
Horizontal compression intensity: 322kPa
Limiting oxygen index(LOI): 30%.
Embodiment 3
Have the High Strength Polyimide foam of regular three-dimensional dimension by the preparation of formula described in embodiment 1, foaming slip total mass and mold cavity volume ratio are M/V=0.15g/cm
3.
Test foam correlated performance and proterties as follows:
Density: 69.56 kilograms per cubic meter
Longitudinal compressive strength: 589kPa
Horizontal compression intensity: 504kPa
Limiting oxygen index(LOI): 30%.
Embodiment 4
Have the High Strength Polyimide foam of regular three-dimensional dimension by the preparation of formula described in embodiment 1, foaming slip total mass and mold cavity volume ratio are 0.18g/cm
3.
Test foam correlated performance and proterties as follows:
Density: 90.32 kilograms per cubic meter
Longitudinal compressive strength: 696kPa
Horizontal compression intensity: 638kPa
Limiting oxygen index(LOI): 31%.
Claims (2)
1. prepare the method with regular three-dimensional dimension polyimide foam for one kind, it is characterized in that: by massfraction be polynary fragrant acid anhydride 150-400 part, polar solvent 100-200 part, fatty alcohol 5-10 part, suds-stabilizing agent 10-20 part, tensio-active agent 10-20 part, catalyzer 5-10 part, deionized water be that 10-20 part and polyisocyanates 300-600 part are prepared in accordance with the following steps
(1) polynary fragrant acid anhydride heating for dissolving and fatty alcohol in polar solvent reacts, and obtains polynary fragrant acid anhydride derivative carboxylicesters solution, specifically comprises:
Polar solvent and the polynary fragrant acid anhydride of 40-160 part is added successively in container, abundant stirring is also heated, when emulsion temp reaches 40-60 DEG C, add fatty alcohol wherein carry out esterification, react the carboxylicesters solution forming clear after 2-3 hour, leave standstill that to be cooled to room temperature stand-by;
(2) expect preparation in vain, specifically comprise:
In carboxylicesters solution, add the polynary fragrant acid anhydride of surplus, catalyzer, tensio-active agent and deionized water under room temperature condition successively, obtain white slip after being uniformly mixed for the white material of foaming;
(3) under room temperature condition of normal pressure, polyisocyanates is added in the white material of foaming and stir, form foaming slip, subsequently foaming slip to be poured in mould and tumble in top cover and form enclosed system, after 2-3 minute, end of processing to be foamed puts into 180-240 DEG C of high temperature oven, hot setting 2-3 hour by filling frothy closed mold;
(4) after having solidified, mould is naturally cooled to room temperature.
2. preparation according to claim 1 has the method for regular three-dimensional dimension polyimide foam, it is characterized in that: by the ratio of change foaming slip total mass M with enclosed system cavity volume V, control density and the compressive strength of polyimide foam, M/V in-scope controls as 0.09-0.18g/cm
3.
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|---|---|---|---|
| CN201510789825.0A CN105315464B (en) | 2015-11-17 | 2015-11-17 | Prepare the method with regular three-dimensional dimension polyimide foam |
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|---|---|---|---|
| CN201510789825.0A CN105315464B (en) | 2015-11-17 | 2015-11-17 | Prepare the method with regular three-dimensional dimension polyimide foam |
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| CN105315464B CN105315464B (en) | 2017-10-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262910A (en) * | 2018-03-07 | 2018-07-10 | 泉州师范学院 | A kind of radio frequency foam device |
| CN110394936A (en) * | 2019-07-31 | 2019-11-01 | 太仓富宇塑胶科技有限公司 | This preparation of the EPP of automotive sunshade panel |
| CN112831024A (en) * | 2021-01-04 | 2021-05-25 | 哈尔滨工程大学 | Safe polyimide-polyurea heat-insulation foam and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184021A (en) * | 1978-10-31 | 1980-01-15 | Nasa | Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN104804190A (en) * | 2015-04-30 | 2015-07-29 | 哈尔滨工程大学 | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method |
| CN104844779A (en) * | 2015-05-18 | 2015-08-19 | 哈尔滨工程大学 | Preparation method for high-strength organosilicone and polyimide compound foam |
-
2015
- 2015-11-17 CN CN201510789825.0A patent/CN105315464B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184021A (en) * | 1978-10-31 | 1980-01-15 | Nasa | Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN104804190A (en) * | 2015-04-30 | 2015-07-29 | 哈尔滨工程大学 | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method |
| CN104844779A (en) * | 2015-05-18 | 2015-08-19 | 哈尔滨工程大学 | Preparation method for high-strength organosilicone and polyimide compound foam |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262910A (en) * | 2018-03-07 | 2018-07-10 | 泉州师范学院 | A kind of radio frequency foam device |
| CN108262910B (en) * | 2018-03-07 | 2023-12-19 | 泉州师范学院 | Radio frequency foaming device |
| CN110394936A (en) * | 2019-07-31 | 2019-11-01 | 太仓富宇塑胶科技有限公司 | This preparation of the EPP of automotive sunshade panel |
| CN112831024A (en) * | 2021-01-04 | 2021-05-25 | 哈尔滨工程大学 | Safe polyimide-polyurea heat-insulation foam and preparation method thereof |
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