CN102838745A - Preparation method of polyimide foam - Google Patents
Preparation method of polyimide foam Download PDFInfo
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- CN102838745A CN102838745A CN2012103496936A CN201210349693A CN102838745A CN 102838745 A CN102838745 A CN 102838745A CN 2012103496936 A CN2012103496936 A CN 2012103496936A CN 201210349693 A CN201210349693 A CN 201210349693A CN 102838745 A CN102838745 A CN 102838745A
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Abstract
The invention provides a preparation method of polyimide foam, which comprises the following steps of: enabling diamine and dianhydride to react in organic solvent to obtain foaming precursors, wherein the diamine at least comprises a kind of diamine with a molecular structure which contains a heteroaromatic ring and a benzene ring; heating the foaming precursors to obtain foaming blocks; and conducting thermal imidization treatment to the foaming blocks to obtain the polyimide foam. The polyimide foam which is prepared by adopting the method has the advantages that the glass transition temperature is high, the heat resistance is good, the mechanical properties are good, and especially under the condition of high temperature, the mechanical properties can still be kept to be good. According to experiments, the compressive strength of the polyimide foam prepared by adopting the method is 0.096-0.127MPa; the glass transition temperature is 290-320DEG C; 5% thermal weight loss temperature is 510-530DEG C; and at 200DEG C, when the volume of the polyimide foam is compressed to 50 percent, the compressive strength of the polyimide foam is 0.092-0.121MPa.
Description
Technical field
The present invention relates to the polyimide material field, particularly the preparation method of polyimide foam.
Background technology
Along with the appearance of " polymer " this type synthetic material, people are incorporated into " porous material " this notion in the synthetic plastics industry, thereby have produced present our each type of foam of available everywhere.
Compared to conventional foam such as urethane, Vilaterm, PS; Polyimide foam has excellent heat resisting, high temperature barrier, noise reduction property, shock resistance, dimensional stability, wave penetrate capability and flame retardant properties; Can be used as heat insulation, sound insulation and fire retardant material, use in fields such as aircraft, spacecraft, weaponry, naval vessel, bullet train and automobiles.
The preparation method of U.S. Pat 3249561 disclosed a kind of polyimide foams; At first obtain polyamic acid by monomer dianhydride and the polymerization of monomer diamines; In the chemical imidization process of polyamic acid, adding can produce the acid of gas, in the curing molding process, produces CO or CO
2Deng gas, foaming obtains polyimide foam.Utilize microwave heating poly amic acid ester salt can obtain the low-density polyimide foam of high foaming in the U.S. Pat 4305796.U.S. Pat 6956066 utilizes pyromellitic acid dianhydride and vulcabond in imidization reaction, to produce CO
2Gas has prepared the foam materials of low density polyimide.But, the bad mechanical property under hot conditions of the polyimide foam material that aforesaid method obtains.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of polyimide foam, good mechanical property under the polyimide foam high-temperature behavior that obtains, and resistance toheat is good.
The invention discloses a kind of preparation method of polyimide foam, may further comprise the steps:
(A) diamines and dianhydride react in organic solvent, obtain the precursor that foams; Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least;
(B) after the foaming precursor that said step (A) is obtained heats, obtain the piece that foams;
(C) the foaming piece that said step (B) is obtained carries out hot imidization to be handled, and obtains polyimide foam.
Preferably; In the said step (A); The diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure is 2,5-two (4-aminophenyl) pyrimidine, 2,5-two (4-aminophenyl) pyridine, the amino benzoxazole of 2-(4-aminophenyl)-6-or the amino benzoglyoxaline of 2-(4-aminophenyl)-6-.
Preferably, in the said step (A), the diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure accounts for 20% ~ 100% of diamines integral molar quantity.
Preferably; In the said step (A); Said dianhydride is a pyromellitic acid anhydride, 4; 4 '-bibenzene tetracarboxylic dianhydride, 3, one or both in 4 '-bibenzene tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride, UVNUL MS-40 tetracarboxylic acid dianhydride, bisphenol A-type phenyl ether dianhydride, triphen diether tetracarboxylic acid dianhydride and the hexafluorodianhydride.
Preferably, said step (A) comprising:
(A1) dianhydride is carried out esterification in lower aliphatic alcohols, obtain mixing solutions;
(A2) diamines is dissolved in organic solvent after, the mixing solutions reaction that obtains with step (A1) obtains polyamic acid solution; Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least;
(A3) the polyamic acid solution concentrate drying that step (A2) is obtained obtains the precursor that foams.
Preferably, in the said step (A2), said reaction times 10-120min, temperature of reaction 20-30 ° of C.
Preferably, in the said step (A), the total mass of said diamines and dianhydride and the mass ratio of organic solvent are 1: (2 ~ 10).
Preferably, in the said step (A), the mol ratio of said diamines and dianhydride is 1: (0.5 ~ 2).
Preferably, in the said step (A1), the mol ratio 1 of said dianhydride and lower aliphatic alcohols: (3 ~ 8).
Preferably, said step B) in, said Heating temperature is 120 ~ 220 ° of C, be 1 ~ 120min heat-up time.
Compared with prior art; At least comprise the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure in the raw material diamines that the present invention selects for use; The diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure has the linearity of biphenyl, rigidity and aromaticity structure; Also pass through the polyimide foam second-order transition temperature height that foamable and hot imidization obtain, good heat resistance with two anhydride reactants.The heteroatoms that comprises in the said molecular structure in the diamines of fragrant heterocycle and phenyl ring has polarity; The molecular chain interphase interaction is strong when finally forming polyimide foam; Therefore, its satisfactory mechanical property especially still can keep the favorable mechanical performance under hot conditions.Experimental result shows that the compressive strength of the polyimide foam that the present invention obtains is 0.096 ~ 0.127MPa; Second-order transition temperature is 290 ℃ ~ 320 ℃; 5% thermal weight loss temperature is 510 ℃ ~ 530 ℃; Under 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.092 ~ 0.121MPa, be under the room temperature polyimide foam volume compression to more than 90% of 50% o'clock compressive strength.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of polyimide foam, may further comprise the steps:
(A) diamines and dianhydride react in organic solvent, obtain the precursor that foams; Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least;
(B) after the foaming precursor that said step (A) is obtained heats, obtain the piece that foams;
(C) the foaming piece that said step (B) is obtained carries out hot imidization to be handled, and obtains polyimide foam.
In the present invention, be raw material with diamines and dianhydride.Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least; The diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure is preferably 2; 5-two (4-aminophenyl) pyrimidine, 2,5-two (4-aminophenyl) pyridine, the amino benzoxazole of 2-(4-aminophenyl)-6-or the amino benzoglyoxaline of 2-(4-aminophenyl)-6-.Said 2,5-two (4-aminophenyl) pyrimidine, 2, the chemical formula of 5-two (4-aminophenyl) pyridine, the amino benzoxazole of 2-(4-aminophenyl)-6-and 2-(4-aminophenyl)-6-amino benzoglyoxaline is as follows.
Said diamines can also advance to select the diamines of other types according to material well known to those skilled in the art except comprising the diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure; As 4; 4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, MDA, Ursol D, mphenylenediamine, diaminobenzophenone, 4,4 '-diaminodiphenylsulfone(DDS), benzidine, 2; 6-diamino-pyridine, 1,6-hexanediamine, siliceous diamines or phosphorous diamines.
The diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure preferably accounts for 20% ~ 100% of diamines integral molar quantity, and more preferably 50% ~ 90%.The present invention does not have particular restriction to the source of said diamines, can be bought by market to obtain.
In the present invention; Said dianhydride there is not particular restriction; Can select according to mode well known to those skilled in the art; Be preferably pyromellitic acid anhydride, 4,4 '-bibenzene tetracarboxylic dianhydride, 3, one or both in 4 '-bibenzene tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride, UVNUL MS-40 tetracarboxylic acid dianhydride, bisphenol A-type phenyl ether dianhydride, triphen diether tetracarboxylic acid dianhydride and the hexafluorodianhydride.
According to the present invention, the present invention reacts diamines and dianhydride in organic solvent, obtain the precursor that foams.In the process of preparation foaming precursor, at first dianhydride is carried out esterification in lower aliphatic alcohols, obtain mixing solutions.Said lower aliphatic alcohols is the Fatty Alcohol(C12-C14 and C12-C18) of 1 ~ 8 carbon atom, is preferably methyl alcohol, ethanol, n-propyl alcohol or butanols.Said dianhydride is preferably than 1 with the mole of lower aliphatic alcohols: (3 ~ 8).The temperature of said esterification is preferably 50 ~ 80 ℃, more preferably 55 ~ 70 ℃.The time of said esterification was reacted more preferably 2 ~ 6 hours 1 hour after being preferably the mixing solutions clarification of esterification again.
In the process of preparation foaming precursor, obtain mixed solution after, diamines is dissolved in organic solvent after, with said mixing solutions reaction, obtain polyamic acid solution.The mol ratio of said diamines and dianhydride is preferably 1: (0.5 ~ 2), more preferably 1: (0.8 ~ 1.2); The total mass of said diamines and dianhydride and the mass ratio of organic solvent are preferably 1: (2 ~ 10), more preferably 1: (4 ~ 8).Said organic solvent is preferably one or both in alcohols or the ether solvent, more preferably one or both in methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, THF, MTBE, dioxane and the glycol dimethyl ether.The effect of said organic solvent is the dissolving diamines, its can with the mixing solutions after joining esterification after diamines mixes again, it also can add when dianhydride carries out esterification.The temperature of said reaction is preferably 20 ~ 30 ℃, and the reaction times is preferably 10 ~ 120 minutes.During said reaction; Better and in preparation foaming piece process impel the foam uniformity in order to make the polyamic acid solution homogeneity that obtains; The preferred tensio-active agent that adds, said tensio-active agent is preferably one or more in ZGK 5, polyether-modified ZGK 5 and the fluorocarbon surfactant.
In the process of preparation foaming precursor, obtain polyamic acid solution after, it is carried out concentrate drying, obtain the precursor that foams.The present invention does not have particular restriction to said drying means, gets final product according to mode well known to those skilled in the art, can be evaporation drying, constant pressure and dry, drying under reduced pressure or heating spraying drying.After obtaining said foaming precursor, preferably it is ground into powder.The present invention does not have particular restriction to the particle diameter of said powder, can select according to particle diameter well known to those skilled in the art.
According to the present invention, behind the foaming precursor that obtains, after said foaming precursor heating, obtain the piece that foams.When said foaming precursor heated, the foaming precursor began to expand gradually, until being solidified into complete foam block.Said foam block contains not the polyamic acid of imidization fully, and fragility is big.The present invention does not have particular restriction to said heating unit, can be electric oven, can be microwave oven yet, if select the microwave oven heating for use, its power is preferably 1000 ~ 10000W.Said Heating temperature is preferably 120 ~ 220 ℃, more preferably 150 ~ 200 ℃, most preferably is 150 ℃.Be preferably 1 ~ 120 minute said heat-up time, more preferably 50 ~ 100 minutes.
According to the present invention, behind the piece that obtains foaming, said foaming piece is carried out hot imidization handle, obtain polyimide foam.Said hot imidization handle with contain in the foam block for the polyamic acid of complete imidization converts polyimide into, from but foam block has flexible mechanical property.Said hot imidization treatment temperature is 300 ℃ ~ 450 ℃, and the time of said hot imidization is 1 ~ 4 hour.
Performance to the polyimide foam that obtains is measured, and the result shows that the compressive strength of the polyimide foam that invention obtains is 0.096 ~ 0.127MPa; Second-order transition temperature is 290 ℃ ~ 320 ℃; 5% thermal weight loss temperature is 510 ℃ ~ 530 ℃; Under 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.092 ~ 0.121MPa, be under the room temperature polyimide foam volume compression to more than 90% of 50% o'clock compressive strength.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of polyimide foam provided by the invention is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Benzophenone tetracarboxylic dianhydride 61.42g (0.1906mol) is joined in the 100ml methyl alcohol, reflux 3 as a child after, system clarification continues reaction 2 hours, obtains mixing solutions.Said mixing solutions temperature drops to room temperature; Add 26.45g (0.1334mol) 4,4-MDA, 15.00g (0.0572mol) 2,5-two (4-aminophenyl) pyrimidine, 1.0g ZGK 5 and 200ml THF; Continue reaction 1 hour, stir and form uniform solution.With above-mentioned solution concentration, drying, obtain the precursor that foams.Said foaming precursor is taped against after crushed the powder bed that forms 2mm on the aluminium sheet.Said powder bed is transferred in the baking oven, and 150 ° of C heated 60 minutes, obtained the piece that foams; Be warmed up to 300 ° of C imidizations 2 hours then, obtain polyimide foam.
Performance to the polyimide foam that obtains is measured, and the result shows that the apparent density of said polyimide foam is 0.021Kg/m
3Glass transition temperature Tg is 301 ° of C, and 5% thermal weight loss temperature is 520 ° of C; Under the room temperature with said polyimide foam volume compression by 50% o'clock, its compressive strength is 0.109MPa; In the time of 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.100MPa.
Embodiment 2
Benzophenone tetracarboxylic dianhydride 61.42g (0.1906mol) is joined in the 100ml methyl alcohol, reflux 3 as a child after, system clarification continues reaction 2 hours, obtains mixing solutions.Said mixing solutions temperature drops to room temperature; Add 26.45g (0.1334mol) 4; The amino benzoxazole of 4'-MDA and 12.88g (0.0572mol) 2-(4-aminophenyl)-6-, 1.0g ZGK 5 and 200ml THF continue reaction 1 hour.Stir and form uniform solution.With above-mentioned solution concentration, drying, obtain the precursor that foams.Said foaming precursor is taped against after crushed the powder bed that forms 2mm on the aluminium sheet.Said powder bed is transferred in the baking oven, and 150 ° of C foamed 60 minutes, obtained the piece that foams; Be warmed up to 300 ° of C imidizations 2 hours then, obtain polyimide foam.
Performance to the polyimide foam that obtains is measured, and the result shows that the apparent density of said polyimide foam is 0.024Kg/m
3Glass transition temperature Tg is 297 ° of C; 5% thermal weight loss temperature is 522 ° of C; Under the room temperature with said polyimide foam volume compression by 50% o'clock, its compressive strength is 0.120MPa; In the time of 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.1MPa.
Embodiment 3
Benzophenone tetracarboxylic dianhydride 61.42g is joined in the 100ml methyl alcohol, reflux 3 as a child after, system clarification continues reaction 2 hours, obtains mixing solutions.Said mixing solutions temperature drops to room temperature, adds 26.45g (0.1334mol) 4, and the amino benzoglyoxaline of 4-MDA and 12.82g 2-(4-aminophenyl)-6-, 1.0g ZGK 5 and 200ml THF continue reaction 1 hour.Stir and form uniform solution.
With above-mentioned solution concentration, drying, obtain the precursor that foams.Said foaming precursor is taped against after crushed the powder bed that forms 2mm on the aluminium sheet.Said powder bed is transferred in the baking oven, and 150 ° of C foamed 60 minutes, obtained the initial foam material; Be warmed up to 300 ° of C imidizations 2 hours then, obtain polyimide foam.
Performance to the polyimide foam that obtains is measured, and the result shows that the apparent density of said polyimide foam is 0.030Kg/m
3Glass transition temperature Tg is 298 ° of C; 5% thermal weight loss temperature is 519 ° of C; Under the room temperature with said polyimide foam volume compression by 50% o'clock, its compressive strength is 0.127MPa; In the time of 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.121MPa.
Embodiment 4
Benzophenone tetracarboxylic dianhydride 61.42g is joined in the 100ml methyl alcohol, reflux 3 as a child after, system clarification continues reaction 2 hours, obtains mixing solutions.Said mixing solutions temperature drops to room temperature; Add 26.45g (0.1334mol) 4,4-MDA and 14.94g (0.0572mol) 2-, 5-two (4-aminophenyl) pyridine, 1.0g ZGK 5 and 200ml THF; Continue stirring reaction 1 hour, and formed uniform solution.
With above-mentioned solution concentration, drying, obtain the precursor that foams.Said foaming precursor is taped against after crushed the powder bed that forms 2mm on the aluminium sheet.Said powder bed is transferred in the baking oven, and 150 ° of C foamed 60 minutes, obtained the initial foam material; Be warmed up to 300 ° of C imidizations 2 hours then, obtain polyimide foam.
Performance to the polyimide foam that obtains is measured, and the result shows that the apparent density of said polyimide foam is 0.026Kg/m
3Glass transition temperature Tg is 312 ° of C; 5% thermal weight loss temperature is 530 ° of C; Under the room temperature with said polyimide foam volume compression by 50% o'clock, its compressive strength is 0.096MPa; In the time of 200 ℃, said polyimide foam volume compression was by 50% o'clock, and its compressive strength is 0.092MPa.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a polyimide foam may further comprise the steps:
(A) diamines and dianhydride react in organic solvent, obtain the precursor that foams; Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least;
(B) after the foaming precursor that said step (A) is obtained heats, obtain the piece that foams;
(C) the foaming piece that said step (B) is obtained carries out hot imidization to be handled, and obtains polyimide foam.
2. preparation method according to claim 1; It is characterized in that; In the said step (A); The diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure is 2,5-two (4-aminophenyl) pyrimidine, 2,5-two (4-aminophenyl) pyridine, the amino benzoxazole of 2-(4-aminophenyl)-6-or the amino benzoglyoxaline of 2-(4-aminophenyl)-6-.
3. preparation method according to claim 1 is characterized in that, in the said step (A), the diamines that comprises fragrant heterocycle and phenyl ring in the said molecular structure accounts for 20% ~ 100% of diamines integral molar quantity.
4. preparation method according to claim 1; It is characterized in that; In the said step (A); Said dianhydride is a pyromellitic acid anhydride, 4,4 '-bibenzene tetracarboxylic dianhydride, 3, one or both in 4 '-bibenzene tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride, UVNUL MS-40 tetracarboxylic acid dianhydride, bisphenol A-type phenyl ether dianhydride, triphen diether tetracarboxylic acid dianhydride and the hexafluorodianhydride.
5. preparation method according to claim 1 is characterized in that, said step (A) comprising:
(A1) dianhydride is carried out esterification in lower aliphatic alcohols, obtain mixing solutions;
(A2) diamines is dissolved in organic solvent after, the mixing solutions reaction that obtains with step (A1) obtains polyamic acid solution; Said diamines comprises the diamines that comprises fragrant heterocycle and phenyl ring in a kind of molecular structure at least;
(A3) the polyamic acid solution concentrate drying that step (A2) is obtained obtains the precursor that foams.
6. preparation method according to claim 5 is characterized in that, in the said step (A2), and said reaction times 10 ~ 120min, 20 ~ 30 ℃ of temperature of reaction.
7. preparation method according to claim 1 is characterized in that, in the said step (A), the total mass of said diamines and dianhydride and the mass ratio of organic solvent are 1: (2 ~ 10).
8. preparation method according to claim 1 is characterized in that, in the said step (A), the mol ratio of said diamines and dianhydride is 1: (0.5 ~ 2).
9. preparation method according to claim 5 is characterized in that, in the said step (A1), and the mol ratio 1 of said dianhydride and lower aliphatic alcohols: (3 ~ 8).
10. preparation method according to claim 1 is characterized in that, said step B) in, said Heating temperature is 120 ~ 220 ° of C, be 1 ~ 120min heat-up time.
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| CN106902652B (en) * | 2017-03-21 | 2019-12-27 | 中国科学院兰州化学物理研究所 | Gas separation membrane with shape memory performance |
| CN108395535A (en) * | 2018-04-03 | 2018-08-14 | 上海市合成树脂研究所有限公司 | A kind of imido preparation method of hot polymerization for laminated product |
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