CN101402795A - Novel fire resistant polyimide foam and method of producing the same - Google Patents

Novel fire resistant polyimide foam and method of producing the same Download PDF

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CN101402795A
CN101402795A CNA2008102268635A CN200810226863A CN101402795A CN 101402795 A CN101402795 A CN 101402795A CN A2008102268635 A CNA2008102268635 A CN A2008102268635A CN 200810226863 A CN200810226863 A CN 200810226863A CN 101402795 A CN101402795 A CN 101402795A
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polyimide foam
bpda
dianhydride
fire resistant
phenylacetylene
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CN101402795B (en
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詹茂盛
潘玲英
王凯
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Shenzhen Hifuture Information Technology Co ltd
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Beihang University
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Abstract

The invention relates a novel high temperature resistant polyimide foam and the preparation process thereof is as follows: (1) firstly, 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride or 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride and another type of aromatic dianhydride are heated and refluxed in a fatty alcohol solution so as to change the tetracarboxylic dianhydride into diacid diester; (2) in accordance with a certain proportion, the obtained diacid diester is synthesized into a precursor solution with one type or more of aromatic diamine and a blocking agent of acetylenyl benzene and a certain quantity of foam stabilizer is added into the solution; (3) the solution is heated to remove tiny molecule volatile matter and obtain a polymide precursor powder; and (4) the precursor powder is filled into a mould to be frothed at high temperature and carries out imidization so as to obtain the polyimide foam. The density of the novel high temperature resistant polyimide foam is 10 kg/m<3> to 500 kg/m<3> and the vitrified transformation temperature is over 350 DEG C; and the foam is characterized by excellent high temperature resistance, low temperature resistance, mechanical properties and functions of anti flaming, heat insulation or noise reduction.

Description

A kind of novel fire resistant polyimide foam and preparation method thereof
Technical field
The present invention relates to a kind of novel fire resistant polyimide foam and preparation method thereof.
Background technology
Compare with conventional foam such as polystyrene, polyethylene, polyurethane foams, polyimide foam has excellent flame, outstanding high and low temperature resistance and good dimensional stability.Therefore; the polyimide foam material is as a member of polyimide material family; since the sixties, Dupont company began development; just caused people's extensive concern; and develop rapidly; be widely used in aspects such as aircraft, spacecraft, weaponry, naval vessel and bullet train at present, as indivedual countries used as the electromagnetic window electromagnetic wave transparent material of the impact absorbing pad of spacecraft low temperature tank lagging material, crash helmet, radome and aircraft corridor structured material etc.
The polyimide foam preparation methods is more at present, U.S. Pat 3249561, US3483144, US4305796, US4439381, US4900761, US6235803, US5994418, US4177333, US5234966, US5077318, European patent EP 0376592, Chinese patent CN1528808, CN101113209 etc. have reported that some prepare the method for polyimide foam material, comprise powder foaming, presoma microballoon foaming, slurry foaming, stick with paste foaming, foam melt method, microwave foaming etc.
Along with the further investigation of polyimide foam, and the continuous expansion of the market requirement, existing at present a few countries is with its polyimide foam commercialization.Up to now, main in the world polyimide foam commodity have: SF series polyimide foam, Germany that du pont company is produced
Figure A20081022686300041
The Rohacell polymethacrylimide foam of company, U.S. Ethyl company produce Polyetherimide foam, the NASA of series polyimide foam, Switzerland AlcanAirex AG company authorize
Figure A20081022686300043
The TEEK of Rexfoam series product and NASA exploitation TMThe series high-performance polyimide foam.The life-time service temperature of these commercial polyimide foams is between 160 ℃~320 ℃.
In view of the requirement of some high-temperature applications, need further to improve the second-order transition temperature of polyimide foam, to satisfy military installations, weaponry and spacecraft etc. to foam materials lightweight, high-strength, high temperature resistant and low temperature resistant requirement.Chinese scholars is being done certain work aspect the raising polyimide foam thermotolerance at present, and has obtained certain effect.U.S. Pat 20020040068, US2003065044 has reported a kind of preparation method of fire resistant polyimide foam, this method is (mainly to be 2 with dianhydride monomer, 3,3 ', 4 '-BPDA) the backflow esterification becomes monoesters or diester in ethanol or methyl alcohol, and in esterification process, add imidization catalyst 1,2 '-methylimidazole, mixture that obtains and Ursol D or 4,4 '-diaminodiphenyl oxide and the reaction of a small amount of 1,3 '-two (3-aminopropyl) tetramethyl-silica alkane obtain the polyimide foam precursor solution, postheating is removed and is desolvated, grinding obtains precursor powder, adopts the microwave heating foaming, finally makes density at 13.5kg/m 3~900kg/m 3Polyimide foam, second-order transition temperature is between 370 ℃~405 ℃.Adopt the HIGH-POWERED MICROWAVES foamable in this method, higher to equipment requirements, increased production cost, simultaneously the poor controllability of foaming process.
U.S. Pat 4978690, US4923907 have reported a kind of by adding the stable on heating method of inorganic nano-particle raising polyimide foam.This method puts it into 400g vermiculite and 400g polyimide prepolymer uniform mixing in the mould then, after the compacting, mould 190.6 ℃ of heating 30min foaming down, is handled 2h down at 260 ℃ then, is cooled to room temperature, and can obtain density is 144kg/m 3The polyimide foam goods.This method is improving the stable on heating while of polyimide foam, has increased the density of polyimide foam, and vermiculite easily mixes inequality with polyimide prepolymer, thereby influences the foamy performance.In addition, Yuan-JyhLeea[Polymer, 2005,46:10056] etc. by using the PEO-POSS template of hydridization, prepared softening temperature between 360 ℃~370 ℃, the temperature of 5wt% thermal weight loss has the polyimide foam of nanoporous between 565 ℃~580 ℃, because formation is nanometer foam, therefore the density of this kind polyimide foam is higher, and this method only is fit to the preparation film article simultaneously.
Chinese patent CN101113209 has reported a kind of preparation method of polysiloxane acid imide foam, and this method adopts situ aggregation method to prepare nanometer SiO 2Micropartical strengthens polyimide foam, and second-order transition temperature has improved 15 ℃~25 ℃, reaches as high as 350 ℃.But this foam still can't satisfy the requirement in some special high temperature fields.
In order to overcome defective of the prior art, the present invention utilizes 2,3,3 ', 4 '-BPDA makes the characteristics that polyimide has good thermoplasticity and high second-order transition temperature, by in polyimide foam presoma building-up process, the phenylacetylene base end-capping reagent of heat cross-linking can take place in introducing, further improve 2,3, the thermotolerance of 3 ', 4 '-BPDA base polyimide foam, its second-order transition temperature can reach more than 450 ℃, and a kind of novel fire resistant polyimide foam of temperature tolerance excellence is provided.
Summary of the invention
The purpose of this invention is to provide polyimide foam of a kind of novel fire resistant and preparation method thereof, promptly, further improve the thermotolerance of polyimide foam by in the building-up process of polyimide foam presoma, introducing the phenylacetylene base end-capping reagent of heat cross-linking type.
The main ingredient of fire resistant polyimide foam of the present invention comprises: (1) one or more aromatic dianhydride A; (2) a kind of or more than one aromatic diamines B; (3) a kind of or more than one phenylacetylene base end-capping reagents C; (4) choose any one kind of them or more than one suds-stabilizing agents.
Wherein, the A component is 2,3,3 ', 4 '-BPDA (a-BPDA); Perhaps 2,3,3 ', 4 '-BPDA and another aromatic dianhydride D, the D component is selected from: 3,3 ', 4, and 4 '-BPDA (s-BPDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (a-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 1,2,4,5-pyromellitic acid dianhydride (PMDA), or its mixture.
The B component comprises: Ursol D (p-PDA), mphenylenediamine (m-PDA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP) or its mixture.
The C component comprises: 4-phenylacetylene phthalic anhydride, 3-phenylacetylene phthalic anhydride, 3-(3-phenylacetylene phenolic group) phthalic anhydride, 4-phenylacetylene aniline, 3-phenylacetylene aniline, 4-styryl-3-Trifluoro methyl benzeneamine, 3-(3-phenylacetylene phenolic group) aniline, 3-amino-4 '-phenylacetylene base benzophenone, 4-amino-4 '-phenylacetylene base benzophenone or its mixture.
Described suds-stabilizing agent comprises: polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, organosilicon glycol copolymer, vinyl polysiloxane, polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, water-soluble polyoxyethylene base class non-ionic type fluorocarbon surfactant and cationic fluorochemical tensio-active agent.
The typical preparation method of novel fire resistant polyimide foam provided by the present invention is as follows:
(1), forms the alcoholic solution of two acid diesters, and when the backflow esterification, add the imide reaction catalyzer with component A (m mole) 70 ℃ of reflux in Fatty Alcohol(C12-C14 and C12-C18);
(2) fatty alcohol solution of B component (n mole), end-capping reagent C (x mole) and optional suds-stabilizing agent are joined the alcoholic solution of above-mentioned (1) described two acid diesters that are cooled to room temperature, reacted 6 hours~24 hours, and prepared the polyimide foam precursor solution;
(3) with the polyimide foam precursor solution described in above-mentioned (2) at 35 ℃~100 ℃ internal heating, remove most of small molecules volatile matter, obtain the polyimide foam precursor powder;
(4) the polyimide foam precursor powder described in above-mentioned (3) is filled in the mould, room temperature rises to 300 ℃~450 ℃, and fire resistant polyimide foam is prepared in foaming, imidization, curing cross-linked 0.5 hour~2 hours.
Among the component A of the present invention 2,3,3 ', 4 '-BPDA (a-BPDA) is 0/100~50/50 with the mol ratio of aromatic dianhydride D, preferred 0/100~30/70, the mol ratio of described component A and B component is m/n=0.5/1.0~1.0/0.5, preferred 0.9/1.0~1.0/0.9, and m/n ≠ 1.0/1.0, the mole number x=2 (m-n) of described end-capping reagent C when n (m>) or 2 (n-m) (when n>m) mole, the addition of described suds-stabilizing agent is 0~5wt% of polyimide foam precursor solution, preferred 0.5wt%~2wt%.
Fatty Alcohol(C12-C14 and C12-C18) described in step (1) and (2) comprises: methyl alcohol, ethanol, n-propyl alcohol, Virahol and butanols.
Imidization reaction catalyzer of the present invention comprises: 1,2-methylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline, isoquinoline 99.9 and substituted pyridines, the pyridine of wherein said replacement can be the 2-picoline, the 3-picoline, the 3-pyridone, 4-pyridone or 4,6-lutidine etc.
The solid content of polyimide precursor solution of the present invention is 8wt%~50wt%, preferred 10wt%~30wt%.
Advantage of the present invention has:
(1) polyimide foam presoma preparation technology is simple;
(2) have 2,3 of unsymmetrical structure by employing, 3 ', 4 '-BPDA when guaranteeing high second-order transition temperature, improves the thermoplasticity of polyimide, reduces melt viscosity, thereby increases foaming power.
(3) by introducing the phenylacetylene base end-capping reagent of heat cross-linking type, in imidization, heat cross-linking takes place, further improve the foamy thermotolerance, and can come the thermotolerance of control foam by the consumption of regulating end-capping reagent.
Fire resistant polyimide foam of the present invention has excellent high-and low-temperature resistance, fire-retardant, heat insulation, anti-acoustic capability, and its density is 10kg/m 3~500kg/m 3Second-order transition temperature is more than 350 ℃; can reach more than 450 ℃; can be used in aircraft, aircraft, weaponry, submarine, naval vessel, automobile or the radar, as the electromagnetic window electromagnetic wave transparent material of the impact absorbing pad of spacecraft low temperature tank lagging material, crash helmet, radome and aircraft corridor structured material etc.
Embodiment
Present invention is described by the following examples; and only be applicable to further specifying to invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add 0.3g2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.
The above-mentioned precursor powder of 1.3g is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 2
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 3
The precursor powder that makes among the 5.2g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 4
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 390 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 5
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 420 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 6
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 30g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) mphenylenediamine (m-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 21.589g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 7
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.359g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.With 3.604g (0.018mol) 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) is dissolved in the 35g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.103g polymethyl siloxane, and add 21.349g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution, 70 ℃ of oven dry subsequently in 1 hour~2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 8
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.33g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.622g (0.015mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 1.932g (0.01mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.094g polymethyl siloxane, and add 28.942g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 9
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 3-phenylacetylene aniline (3-PEA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 10
In the single port bottle, 5.296g (0.018mol) a-BPDA and 0.993g (0.004mol) 3-phenylacetylene phthalic anhydride (3-PEPA) are joined in the 40g methyl alcohol, add the 0.296g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h, obtain 2,3,3 ', the methanol solution of 4 '-biphenyl acid diester (a-BPDE) and 3-phenylacetylene benzene methyl (3-PEPE) is cooled to room temperature with it then.2.163g (0.02mol) Ursol D (p-PDA) is dissolved in the 25g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add the 0.084g polymethyl siloxane, and add 11.068g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution in 1 hour~2 hours, and 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 11
In the single port bottle, 5.296g (0.018mol) a-BPDA and 0.993g (0.004mol) 4-phenylacetylene phthalic anhydride (4-PEPA) are joined in the 40g methyl alcohol, add the 0.296g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h, obtain 2,3,3 ', the methanol solution of 4 '-biphenyl acid diester (a-BPDE) and 4-phenylacetylene benzene methyl (4-PEPE) is cooled to room temperature with it then.2.163g (0.02mol) Ursol D (p-PDA) is dissolved in the 25g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add the 0.084g polymethyl siloxane, and add 11.068g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution in 1 hour~2 hours, and 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 12
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 1.045g (0.004mol) 4-styryl-3-Trifluoro methyl benzeneamine (3-FPA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour~2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 13
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 1.141g (0.004mol) 3-(3-phenylacetylene phenolic group) aniline (PEPOA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour~2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 14
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, adding 1.189g (0.004mol) 3-amino-4 '-phenylacetylene base benzophenone (3A4 ' PEB) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour~2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 15
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, adding 1.189g (0.004mol) 4-amino-4 '-phenylacetylene base benzophenone (4A4 ' PEB) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour~2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 16
In the single port bottle, with 4.708g (0.016mol) a-BPDA and 1.289g (0.004mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA) joins in the 40g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.087g polymethyl siloxane, and add 18.444g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 17
In the single port bottle, 5.884g (0.02mol) a-BPDA is joined in the 15g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, the methanol solution of 3 ', 4 '-biphenyl acid diester (a-BPDE) is cooled to room temperature with it then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 15g methyl alcohol, add in the methanol solution of the a-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours~8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours~4 hours, add the 0.086g polymethyl siloxane, and add 4.412g methyl alcohol, the solid content of adjusting precursor solution is 20wt%, continue reaction and obtained precursor solution in 1 hour~2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Density and second-order transition temperature by the foregoing description 1 to embodiment 17 gained polyimide foam are illustrated in the table 1.
The proportioning and the foamy second-order transition temperature (Tg) of table 1 preparation fire resistant polyimide foam
Example Foam formation/mol ratio The imidization temperature/℃ Density/kgm -3 Tg/℃
1 a-BPDA/p-PDA/4-PEA=10∶9∶2 360 30 418
2 a-BPDA/p-PDA/4-PEA=10∶9∶2 360 60 418
3 a-BPDA/p-PDA/4-PEA=10∶9∶2 360 120 418
4 a-BPDA/p-PDA/4-PEA=10∶9∶2 390 60 430
5 a-BPDA/p-PDA/4-PEA=10∶9∶2 420 60 >450
6 a-BPDA/m-PDA/4-PEA=10∶9∶2 420 60 427
7 a-BPDA/4,4’-ODA/4-PEA=10∶9∶2 420 60 365
8 a-BPDA/p-PDA/4-PEA=4∶3∶2 420 60 >450
9 a-BPDA/p-PDA/4-PEA=10∶9∶2 420 60 >450
10 a-BPDA/p-PDA/3-PEPA=10∶9∶2 420 60 >450
11 a-BPDA/p-PDA/4-PEPA=10∶9∶2 420 60 >450
12 a-BPDA/p-PDA/3-FPA=10∶9∶2 420 60 >450
13 a-BPDA/p-PDA/PEPOA=10∶9∶2 420 60 >450
14 a-BPDA/p-PDA/3A4’PEA=10∶9∶2 420 60 >450
15 a-BPDA/p-PDA/4A4’PEA=10∶9∶2 420 60 >450
16 a-BPDA/s-BTDA/ p-PDA/4-PEA=8∶2∶9∶2 420 60 436
17 a-BPDA/p-PDA/4-PEA=10∶9∶2 420 60 >450

Claims (10)

1, a kind of fire resistant polyimide foam is characterized in that: the density of described fire resistant polyimide foam is at 10kg/m 3~500kg/m 3, second-order transition temperature can reach more than 450 ℃ more than 350 ℃.
2, fire resistant polyimide foam as claimed in claim 1, it is characterized in that: described fire resistant polyimide foam is to be prepared from by aromatic dianhydride A, aromatic diamines B and end-capping reagent C, wherein the A component is by 2,3,3 ', 4 '-BPDA (a-BPDA) or 2,3,3 ', 4 '-BPDA and another aromatic dianhydride D form; Described B component is selected from: Ursol D (p-PDA), mphenylenediamine (m-PDA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP) or its mixture; Described end-capping reagent C is the phenylacetylene base end-capping reagent.
3, fire resistant polyimide foam as claimed in claim 2 is characterized in that: described phenylacetylene base end-capping reagent is selected from: 4-phenylacetylene phthalic anhydride, 3-phenylacetylene phthalic anhydride, 3-(3-phenylacetylene phenolic group) phthalic anhydride, 4-phenylacetylene aniline, 3-phenylacetylene aniline, 4-styryl-3-Trifluoro methyl benzeneamine, 3-(3-phenylacetylene phenolic group) aniline, 3-amino-4 '-phenylacetylene base benzophenone, 4-amino-4 '-phenylacetylene base benzophenone or its mixture; Described aromatic dianhydride D is selected from: 3,3 ', 4,4 '-BPDA (s-BPDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (a-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 1,2,4,5-pyromellitic acid dianhydride (PMDA).
4, as each described fire resistant polyimide foam of claim 2~3, it is characterized in that: the D component is selected from: 3,3 ', 4,4 '-BPDA (s-BPDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (a-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 1,2,4,5-pyromellitic acid dianhydride (PMDA), or its mixture.
5, as each described fire resistant polyimide foam of claim 2~4, it is characterized in that: among the component A 2,3,3 ', 4 '-BPDA (a-BPDA) is 0/100~50/50 with the mol ratio of aromatic dianhydride D.
6, as the preparation method of each described fire resistant polyimide foam of claim 1~5, it is characterized in that: may further comprise the steps:
(1), forms the alcoholic solution of two acid diesters, and when the backflow esterification, add the imide reaction catalyzer with aromatic dianhydride A reflux in Fatty Alcohol(C12-C14 and C12-C18);
(2) fatty alcohol solution, the end-capping reagent C of aromatic diamines B joined the alcoholic solution of above-mentioned (1) described two acid diesters that are cooled to room temperature, reacted 6 hours~24 hours, prepare the polyimide foam precursor solution;
(3) with the polyimide foam precursor solution described in above-mentioned (2) at 35 ℃~100 ℃ internal heating, remove the small molecules volatile matter, obtain the polyimide foam precursor powder;
(4) the polyimide foam precursor powder described in above-mentioned (3) is filled in the mould, inserts in the oven heat, room temperature rises to 300 ℃~450 ℃, and fire resistant polyimide foam is prepared in foaming, imidization, curing cross-linked 0.5 hour~2 hours.
7, preparation method as claimed in claim 6 is characterized in that: mol ratio m/n=0.5/1.0~1.0/0.5 of described aromatic dianhydride A and aromatic diamines B, and m/n ≠ 1.0/1.0; When m>n, the mole number x=2 (m-n) of described end-capping reagent; When n>m, the mole number x=2 (n-m) of described end-capping reagent.
8, as claim 6 or 7 described preparation methods, it is characterized in that: in step (2), also add suds-stabilizing agent.
9, as each described preparation method of claim 6~8, it is characterized in that: described Fatty Alcohol(C12-C14 and C12-C18) is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol and butanols.
10, as each described preparation method of claim 6~9, it is characterized in that: described imidization reaction catalyzer is selected from 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline, isoquinoline 99.9 and substituted pyridines.
CN2008102268635A 2008-11-19 2008-11-19 Novel fire resistant polyimide foam and method of producing the same Expired - Fee Related CN101402795B (en)

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US20170150651A1 (en) * 2015-11-19 2017-05-25 Boyd Corporation Densified foam for thermal insulation in electronic devices
US10448541B2 (en) * 2015-11-19 2019-10-15 Boyd Corporation Densified foam for thermal insulation in electronic devices
CN108017786A (en) * 2017-12-24 2018-05-11 桂林理工大学 The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride
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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