CN105175724A - Preparation method of ultralow-density polyimide porous material by one-step process - Google Patents
Preparation method of ultralow-density polyimide porous material by one-step process Download PDFInfo
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- CN105175724A CN105175724A CN201510732330.4A CN201510732330A CN105175724A CN 105175724 A CN105175724 A CN 105175724A CN 201510732330 A CN201510732330 A CN 201510732330A CN 105175724 A CN105175724 A CN 105175724A
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Abstract
The invention discloses a preparation method of an ultralow-density polyimide porous material by a one-step process. The temperature of the foaming black material and white material is enhanced to effectively enhance the foaming ratio in the free foaming process and preliminarily lowering the material density; and the porous material intermediate is reexpanded by vacuum treatment to further lower the density, thereby finally obtaining the ultralow-density one-step-process polyimide porous material. The porous material prepared by the method is a semiclosed-cell structure with uniform pore structure and soft texture, and the density is less than 10kg/m<3>. As the temperature of the slurry gradually increases and the vacuum degree in the vacuum treatment process gradually increases, the material density tends to gradual decrease. The method has the advantages of simple preparation technique and low manufacturing cost, can easily implement industrial production, further lowers the product density, achieves the goal of the invention, and can further display the performance advantage of light weight of the one-step-process polyimide porous material.
Description
Technical field
That the present invention relates to is a kind of preparation method, particularly a kind of one-step preppn process of extremely-low density polyimide porous material of low density porous material.
Background technology
Polyimide porous material is the light porous material that a class is matrix resin with high-performance polymer material-polyimide, owing to having the advantages such as lightweight, high-low temperature resistant, heat insulating, fire-retardant, resistance to irradiation, the sophisticated technology fields such as aerospace, naval vessel, bullet train are widely used in.The technology of preparing of current polyimide porous material mainly comprises single stage method technology of preparing and two-step approach technology of preparing, although the polyimide porous material high comprehensive performance obtained by two-step approach technology of preparing, but the factors such as complicated process of preparation, the prices of raw and semifnished materials are expensive directly results in product price and remain high, and therefore limit the widespread use of such material at civil area always.The single stage method technology of preparing of polyimide porous material is found in the patent US3300420 of USS oil company application the earliest, and the patent such as US6596066, US7541388 has carried out series report to this technology again subsequently.Single stage method technology of preparing is shaping rapidly by room temperature free foaming process, porous material is obtained again through subsequent high temperature solidification, preparation flow is simple, the prices of raw and semifnished materials are cheap, final product price decline degree compared with two-step approach, up to 70-90%, is conducive to the Application Areas widening polyimide porous material further.Although single stage method technology of preparing preparation technology flow process is simple, product price is cheap, but the polyimide porous material density at present obtained by single stage method technology of preparing generally at 13 kilograms more than every cubic metre higher than the polyimide porous material obtained by two-step approach technology of preparing, do not belong to the category of extremely-low density porous material, not only can not meet the extreme requirement of association area to porous material lightweight performance, be also unfavorable for the further reduction of material preparation cost simultaneously.
Summary of the invention
The object of the present invention is to provide one to obtain is half unicellular structure, uniform foam cell, quality softness, and apparent density can reach the one-step preppn process of the extremely-low density polyimide porous material of the porous material of extremely-low density rank.
The one-step preppn process of extremely-low density polyimide porous material of the present invention comprises the following steps, and the material proportion wherein related to is ratio of quality and the number of copies;
(1) in container, add 10-15 part polar solvent and the polynary fragrant acid anhydride of 4-10 part successively, stir and be warming up to 50-120 DEG C of stopping heating, adding 1-2 part fatty alcohol refuxing esterification, form fragrant acid anhydride derivative carboxylicesters solution;
(2) in 10-30 part fragrant acid anhydride derivative carboxylicesters solution, add 0.5-2 part catalyzer, 1-3 part suds-stabilizing agent, 1-3 part tensio-active agent and 2-5 part deionized water successively and be mixed with the white material of foaming;
(3) respectively white for the foaming of step (2) gained material and 20-40 part polyisocyanates are heated to 30-60 DEG C under condition of normal pressure;
(4) poured into by polyisocyanates in the white material of foaming and obtain mixing solutions, being stirred by mixing solutions and pouring free foaming in mould into obtains porous material intermediate;
(5) porous material intermediate is placed in the vacuum drying oven being heated to 80-120 DEG C in advance and carries out vacuum-treat, vacuum tightness remains on 0.05-0.1MPa;
(6) porous material intermediate proceeds to solidification in the air dry oven of 180 DEG C and obtains polyimide porous material in 2 hours process 1-1.5 hour in vacuum drying oven after.
The one-step preppn process of extremely-low density polyimide porous material of the present invention can also comprise:
1, described 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 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 polarity is molten is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
3, described fatty alcohol is methyl alcohol or ethanol.
4, described suds-stabilizing agent is non-hydrolytic type water soluble polyether siloxanes (AK8805, DC193, L580); Tensio-active agent comprises: non-ion fluorin carbon surface active agent (
fS-300,
fSO-100), 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; Deionized water is whipping agent.
6, described polyisocyanates is diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI) or polyphenyl polymethylene polyisocyanates (PAPI).
7, the intensification described in step (1) completed in 30 minutes.
The principal feature of the one-step preppn process of extremely-low density polyimide porous material of the present invention is: first foaming slip temperature from ambient is increased to 30-60 DEG C, effectively raise the expansion ratio in free foaming process, density of material is tentatively reduced; Then porous material intermediate is placed in the vacuum drying oven that vacuum tightness is 0.05-0.1MPa, temperature is 80-120 DEG C to process, through reexpanding, density of material being reduced further, obtaining the single stage method polyimide porous material with extremely-low density finally by hot setting.Porous material prepared by described method is half unicellular structure, uniform foam cell, quality softness, and apparent density can reach extremely-low density rank.Present method preparation technology is simple, cheap for manufacturing cost, be easy to suitability for industrialized production, special dimension can be met to the light-weighted extreme requirement of porous material simultaneously, reach the object of invention, the light-weighted performance advantage of single stage method polyimide porous material can be highlighted further.
Compared with prior art, the mode that the present invention adopts raising slurry temperature and vacuum-treat to combine, makes the density of single stage method polyimide foam porous material be significantly reduced, reaches extremely-low density rank, highlighted its lightweight feature further.Effectively can not only reduce preparation cost, meet the extreme requirement of special dimension to porous material density simultaneously.Present method preparation technology is simple, cheap for manufacturing cost, is conducive to suitability for industrialized production and widespread use.Polyimide porous material density obtained by method of the present invention is less than 10 kilograms every cubic metre, reaches extremely-low density rank.
Embodiment
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 130 grams of N-Methyl pyrrolidone and 65 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 90 DEG C, treat 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride (BTDA) dissolves completely, heating is stopped when solution is clear state, in turbid liquid, 12 grams of methyl alcohol are dropwise instilled with constant pressure funnel when temperature is down to about 50 DEG C, rate of addition controls at 1-5 milliliter per minute, make 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride (BTDA) starts to carry out esterification, reaction to be esterified is carried out completely, solution is again after clear, magnetic stirrer stops stirring, above-mentioned solution left standstill is down to room temperature, obtained close to water white two acid diesters solution, lucifuge stores stand-by.
Take 20 grams of above-mentioned two acid diesters solution in disposal plastic cup, add 2 grams of suds-stabilizing agents, 2 grams of polyoxyethylene surfactant, 1.5 grams of catalyst compounded, 2.5 grams of deionized waters successively, the foaming forming clear after fully stirring is expected in vain.Take 30 grams of PAPI and be placed in another disposal plastic cup, the plastic cup that the white material of foaming and PAPI are housed is placed in oil bath pan and heats.Take out after two kinds of component temperature are increased to 45 degrees Celsius, PAPI is poured into rapidly in the disposal plastic cup that the white material of foaming is housed, even with electric stirring oar rapid stirring, pour rapidly free foaming in mould when thing to be mixed starts to foam and hoists into and obtain porous material intermediate.Porous material intermediate is proceeded to immediately in the vacuum drying oven being warming up to 120 DEG C in advance, regulate vacuum tightness in vacuum drying oven to carry out vacuum-treat to 0.05MPa to porous material intermediate, continue one hour.The electric drying oven with forced convection subsequently the porous material intermediate handled well being placed in 180 DEG C solidifies 120 minutes, obtained single stage method polyimide porous material.Polyimide porous material density obtained by test result display is less than 10 kilograms every cubic metre, reaches extremely-low density rank.
Embodiment 2
In 250ml there-necked flask, add 100 grams of N-Methyl pyrrolidone and 42 grams of pyromellitic acid dianhydrides (PMDA) add magneton, connect reflux condensing tube and pass into water coolant, under magnetic stirrer effect, abundant stirring is slowly warming up to 50 DEG C, in turbid liquid, 12 grams of methyl alcohol are dropwise instilled with constant pressure funnel, rate of addition controls at 1-5 milliliter per minute, pyromellitic acid dianhydride (PMDA) is made to start to carry out esterification, reaction to be esterified is carried out completely, solution is again after clear, magnetic stirrer stops stirring, above-mentioned solution left standstill is down to room temperature, obtained close to water white two acid diesters solution, lucifuge stores stand-by.
Take 20 grams of above-mentioned two acid diesters solution in disposal plastic cup, add 2 grams of suds-stabilizing agents, 2 grams of polyoxyethylene surfactant, 1.5 grams of catalyst compounded, 2.5 grams of deionized waters successively, the foaming forming clear after fully stirring is expected in vain.Take 25 grams of PAPI and be placed in another disposal plastic cup, the plastic cup that the white material of foaming and PAPI are housed is placed in oil bath pan and heats.Take out after two kinds of component temperature are increased to 55 degrees Celsius, PAPI is poured into rapidly in the disposal plastic cup that the white material of foaming is housed, even with electric stirring oar rapid stirring, pour rapidly free foaming in mould when thing to be mixed starts to foam and hoists into and obtain porous material intermediate.Porous material intermediate is proceeded to immediately in the vacuum drying oven being warming up to 120 DEG C in advance, regulate vacuum tightness in vacuum drying oven to carry out vacuum-treat to 0.08MPa to porous material intermediate, continue one hour.The electric drying oven with forced convection subsequently the porous material intermediate handled well being placed in 180 DEG C solidifies 120 minutes, obtained single stage method polyimide porous material.Polyimide porous material density obtained by test result display is less than 10 kilograms every cubic metre, reaches extremely-low density rank.
Embodiment 3
Take two acid diesters solution in 20 grams of embodiments 1 and, in disposal plastic cup, add 2 grams of suds-stabilizing agents, 2 grams of polyoxyethylene surfactant, 1.5 grams of catalyst compounded, 2.5 grams of deionized waters successively, the foaming forming clear after fully stirring is expected in vain.Take 30 grams of PAPI and be placed in another disposal plastic cup, the plastic cup that the white material of foaming and PAPI are housed is placed in oil bath pan and heats.Take out after two kinds of component temperature are increased to 35 degrees Celsius, PAPI is poured into rapidly in the disposal plastic cup that the white material of foaming is housed, even with electric stirring oar rapid stirring, pour rapidly free foaming in mould when thing to be mixed starts to foam and hoists into and obtain porous material intermediate.Porous material intermediate is proceeded to immediately in the vacuum drying oven being warming up to 120 DEG C in advance, regulate vacuum tightness in vacuum drying oven to carry out vacuum-treat to 0.05MPa to porous material intermediate, continue one hour.The electric drying oven with forced convection subsequently the porous material intermediate handled well being placed in 180 DEG C solidifies 120 minutes, obtained single stage method polyimide porous material.Polyimide porous material density obtained by test result display is about 10 kilograms every cubic metre, reaches extremely-low density rank.
Embodiment 4
Take two acid diesters solution in 20 grams of embodiments 2 and, in disposal plastic cup, add 2 grams of suds-stabilizing agents, 2 grams of polyoxyethylene surfactant, 1.5 grams of catalyst compounded, 2.5 grams of deionized waters successively, the foaming forming clear after fully stirring is expected in vain.Take 20 grams of PAPI and 10 gram MDI and be placed in another disposal plastic cup, the plastic cup that the white material of foaming and isocyanic ester are housed is placed in oil bath pan and heats.Take out after two kinds of component temperature are increased to 60 degrees Celsius, isocyanic ester mixed solution is poured into rapidly in the disposal plastic cup that the white material of foaming is housed, even with electric stirring oar rapid stirring, pour rapidly free foaming in mould when thing to be mixed starts to foam and hoists into and obtain porous material intermediate.Porous material intermediate is proceeded to immediately in the vacuum drying oven being warming up to 120 DEG C in advance, regulate vacuum tightness in vacuum drying oven to carry out vacuum-treat to 0.06MPa to porous material intermediate, continue one hour.The electric drying oven with forced convection subsequently the porous material intermediate handled well being placed in 180 DEG C solidifies 120 minutes, obtained single stage method polyimide porous material.Polyimide porous material density obtained by test result display is less than 10 kilograms every cubic metre, reaches extremely-low density rank.
Embodiment 5
In 250ml there-necked flask, add 130 grams of N-Methyl pyrrolidone, 33 gram 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride (BTDA) and 22 grams of pyromellitic acid dianhydrides (PMDA) add magneton, connect reflux condensing tube and pass into water coolant, under magnetic stirrer effect, abundant stirring is slowly warming up to 50 DEG C, in turbid liquid, 12 grams of methyl alcohol are dropwise instilled with constant pressure funnel, rate of addition controls at 1-5 milliliter per minute, acid anhydrides is made to start to carry out esterification, reaction to be esterified is carried out completely, solution is again after clear, magnetic stirrer stops stirring, above-mentioned solution left standstill is down to room temperature, obtained close to water white two acid diesters solution, lucifuge stores stand-by.
Take 20 grams of above-mentioned two acid diesters solution in disposal plastic cup, add 2 grams of suds-stabilizing agents, 2 grams of polyoxyethylene surfactant, 1.5 grams of catalyst compounded, 2.5 grams of deionized waters successively, the foaming forming clear after fully stirring is expected in vain.Take 30 grams of PAPI and be placed in another disposal plastic cup, the plastic cup that the white material of foaming and PAPI are housed is placed in oil bath pan and heats.Take out after two kinds of component temperature are increased to 60 degrees Celsius, PAPI is poured into rapidly in the disposal plastic cup that the white material of foaming is housed, even with electric stirring oar rapid stirring, pour rapidly free foaming in mould when thing to be mixed starts to foam and hoists into and obtain porous material intermediate.Porous material intermediate is proceeded to immediately in the vacuum drying oven being warming up to 120 DEG C in advance, regulate vacuum tightness in vacuum drying oven to carry out vacuum-treat to 0.08MPa to porous material intermediate, continue one hour.The electric drying oven with forced convection subsequently the porous material intermediate handled well being placed in 180 DEG C solidifies 120 minutes, obtained single stage method polyimide porous material.Polyimide porous material density obtained by test result display is less than 10 kilograms every cubic metre, reaches extremely-low density rank.
Claims (6)
1. an one-step preppn process for extremely-low density polyimide porous material, is characterized in that comprising the following steps, and the material proportion wherein related to is ratio of quality and the number of copies;
(1) in container, add 10-15 part polar solvent and the polynary fragrant acid anhydride of 4-10 part successively, stir and be warming up to 50-120 DEG C of stopping heating, adding 1-2 part fatty alcohol refuxing esterification, form fragrant acid anhydride derivative carboxylicesters solution;
(2) in 10-30 part fragrant acid anhydride derivative carboxylicesters solution, add 0.5-2 part catalyzer, 1-3 part suds-stabilizing agent, 1-3 part tensio-active agent and 2-5 part deionized water successively and be mixed with the white material of foaming;
(3) respectively white for the foaming of step (2) gained material and 20-40 part polyisocyanates are heated to 30-60 DEG C under condition of normal pressure;
(4) poured into by polyisocyanates in the white material of foaming and obtain mixing solutions, being stirred by mixing solutions and pouring free foaming in mould into obtains porous material intermediate;
(5) porous material intermediate is placed in the vacuum drying oven being heated to 80-120 DEG C in advance and carries out vacuum-treat, vacuum tightness remains on 0.05-0.1MPa;
(6) porous material intermediate proceeds to solidification in the air dry oven of 180 DEG C and obtains polyimide porous material in 2 hours process 1-1.5 hour in vacuum drying oven after.
2. the one-step preppn process of extremely-low density polyimide porous material according to claim 1, is characterized in that: the intensification described in step (1) completed in 30 minutes.
3. the one-step preppn process of extremely-low density polyimide porous material according to claim 2, is characterized in that: described 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 anhydride, three trimellitic acid 1,2-anhydrides-1,3,5-benzene three ester or 1,3,5-tri-oxygen-three (4-phthalic anhydride) benzene.
4. the one-step preppn process of extremely-low density polyimide porous material according to claim 3, is characterized in that: described polarity is molten is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
5. the one-step preppn process of extremely-low density polyimide porous material according to claim 4, is characterized in that: described catalyzer is trolamine, triethylenediamine, stannous octoate, dibutyl tin laurate or Dabco33-LV; Deionized water is whipping agent.
6. the one-step preppn process of extremely-low density polyimide porous material according to claim 5, is characterized in that: described polyisocyanates is diphenylmethanediisocyanate, tolylene diisocyanate or polyphenyl polymethylene polyisocyanates.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522621A (en) * | 2017-10-10 | 2017-12-29 | 东华大学 | A kind of preparation method of photoinduction antibacterial finishing agent benzophenone tetracarboxylic ester |
| 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 |
| CN112126110A (en) * | 2020-08-31 | 2020-12-25 | 哈尔滨工程大学 | Polyimide sound absorption foam with spherical pit microstructure and preparation method thereof |
| CN112316465A (en) * | 2019-08-05 | 2021-02-05 | 哈尔滨工程大学 | Distillation flask coated with polyimide foam layer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN107522621B (en) * | 2017-10-10 | 2021-04-02 | 东华大学 | Preparation method of photo-induced antibacterial finishing agent benzophenone tetraformate |
| CN112316465A (en) * | 2019-08-05 | 2021-02-05 | 哈尔滨工程大学 | Distillation flask coated with polyimide foam layer and preparation method thereof |
| CN112126110A (en) * | 2020-08-31 | 2020-12-25 | 哈尔滨工程大学 | Polyimide sound absorption foam with spherical pit microstructure and preparation method thereof |
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Application publication date: 20151223 |