CN102093714B - Light flexible polymide foam material and preparation method thereof - Google Patents
Light flexible polymide foam material and preparation method thereof Download PDFInfo
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- CN102093714B CN102093714B CN2010106002572A CN201010600257A CN102093714B CN 102093714 B CN102093714 B CN 102093714B CN 2010106002572 A CN2010106002572 A CN 2010106002572A CN 201010600257 A CN201010600257 A CN 201010600257A CN 102093714 B CN102093714 B CN 102093714B
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Abstract
The invention discloses a light flexible polymide foam material and a preparation method thereof. The light flexible polymide foam material is obtained by reaction and solidification of hyperbranched aromatic polyamide, a catalyst, a surface active agent, an accessory ingredient and isocyanate, wherein the hyperbranched aromatic polyamide is formed by aromatic triamine together with aromatic dianhydride and/or aromatic acid ester. The intermediate section of the molecular structure is a hyperbranched section formed by the aromatic triamine together with the aromatic dianhydride and/or the aromatic acid ester, the side chain of the molecular structure is a cross-linking or/and linear section formed by aromatic dianhydride and/or aromatic acid ester together with isocyanate. The polymide foam material is simple in preparation process, the shrinkage percentage of the polymide foam material is minus 35.34%-21.75%, the density of the polymide foam material is 6.0 kg/m<3>-31.0 kg/m<3>, and the glass-transition temperature of the polymide foam material is 235 DEG C-320 DEG C; and the polymide foam material is a flexible sound-absorbing noise-reducing polymer foam material and is mainly suitable for the fields of aerospace, ships and electronic industry.
Description
Technical field
The present invention relates to a kind of light flexible polyimide foam material and preparation method thereof.
Background technology
The polyimide foam material is a kind ofly novel have particular chemical structure, high-low temperature resistant zone and be the light material that-250 ℃～450 ℃, unharmful substance discharge, performance such as have that excellent heat insulation and acoustic absorption performance, excellent dielectric properties, good gentle elasticity, intensity can design, anti-irradiation, anti-solvent, difficult combustion and low is fuming.It serves many purposes the decision of the performance of polyimide foam material, at present more and more as the critical material of aspects such as the load of high-technology fields such as aerospace, naval vessels and microelectronics, heat insulation, damping noise reduction and insulation.
The polyimide foam preparation methods is more at present; U.S. Pat 3249561, US3310506, and English Patent GB999578 through the preparation polyamic acid solution; Add chemical imidization reagent then, vigorous stirring is introduced bubble, preparation sheet polyimide foam.But the inhomogeneous and chemical foaming agent in the foam materials aperture of this method preparation remains in the foam easily.
US3483144 adopts the Prepared by Ball Milling polyimide foam.Dianhydride and two amine solvents and end reaction generate the water foaming and form foam under the ball milling molten state.The defective of this method is that abscess is inhomogeneous, poor dimensional stability, and the whipping agent water-content that reaction produces seldom only can prepare density and be about 430kg/m
3The high-density polyimide foam materials.
US4305796, US4439381, US4822537 replace baking oven for heating to prepare polyimide foam through the microwave foaming technique, and its foaming and imidization speed are fast, and efficient is high, but the foam defective of this method preparation is many, and density unevenness is even.
European patent EP 0376592 discloses the method that a kind of extrusion foaming prepares polyimide foam.TPI is melt extruded in 380 ℃～410 ℃ TRs, through adding whipping agent or decompression cooling foaming at mouth mould place.This law limitation is the difficult controls of processing condition, and foam aperture is inhomogeneous.
WO9962984, U.S. Pat 4656198, US4670478, US4647597, US4425441, US6133330, US6180746B1, US6084000, US6180746B1, US6084000 and Chinese patent CN101402795A, CN200710119168.4 have reported that employing powder/microballoon foaming prepares the method for polyimide foam.With dianhydride and verivate esterification in the solution of small molecular alcohol and ether thereof; In esterification solution, add diamines then and react, obtain polyamic acid prepolymer solution, again through dry, pulverizing; Obtain polyamic acid presoma powder, high temperature prepares polyimide microsphere and polyimide foam then.
US4900761, US5122546A, US5096932, US5234966, US5298531, US4952611A, US5064867 are earlier with dianhydride esterification in alcohol and water; Add preparation polyimide precursor solutions such as diamines, whipping agent then; At a certain temperature the presoma powder is processed in the heating of part precursor solution; Then presoma powder and water or polyimide precursor solution are mixed and made into soup compound; In microwave oven or baking oven, add the hot preparation polyimide foam again, or directly polyimide precursor solution is carried out pyroprocessing and prepare polyimide foam.Whipping agent can cause foam to produce non-homogeneous vesicular structure as an independent subject in this method, simultaneously can residual whipping agent on cell wall.
CN1528808A discloses the method that a kind of polyethers coupling precursor process prepares polyimide foam.With dianhydride esterification in small molecular alcohol and monohydroxy polyethers, add diamines then and small molecules ether fully reacts, to pulverize after the oven dry, high temperature is preparation polyimide microsphere and polyimide foam down.
CN101456967A makes composite powder through pore-creating agent is joined in the TPI powder, then preparation polyimide porous material under the high temperature of the high pressure of 20MPa～50MPa and 280 ℃～330 ℃.The defective of this method is that blow(ing)pressure is big, temperature is high, power consumption and density of material are big.
Adopt two acid diesters midbodys and diamine reactant to prepare polyamic acid precursor powder or microballoon in the aforesaid method; The polyimide foam over-all properties of high temperature preparation is better then; But can not obtain the polyimide foam of wide density range, especially can not obtain low-density goods; Midbody is wayward simultaneously, and by product is more, can generate the final foaming properties of influence such as three esters or four esters; In addition, the foam of this method preparation is mainly closed pore, heat insulation polyimide foam, and is irrelevant with content of the present invention.
U.S. Pat 5900440, US4177333 are through joining catalyzer in the mixture of dianhydride and isocyanic ester, and pyroprocessing prepares polyimide foam then.Under lower temperature, stir the mixture earlier, as the CO of reaction generation
2When burst size was the 1wt%～8wt% of mixture total mass, termination reaction also shifted out mixture from container, pulverized or directly poured high temperature foaming in the mould into, obtained the polyimide foam material.This method can prepare low density perforate polyimide foam, but defective is a complex process, CO
2Burst size is wayward, and foam contraction is serious.
US5153234 discloses and a kind of dianhydride, isocyanic ester, catalyzer etc. has been mixed in container, pours into then in the mould of preheating, 200 ℃～250 ℃ methods that keep obtaining in 5 minutes～15 minutes polyimide foam down.This method can prepare low-density polyimide foam material, but defective is that the material degree of imidisation is not enough, and foam falls slag, and is yielding, and scrap rate is high.
US3772216 is through mixing dianhydride, isocyanic ester, catalyzer, tensio-active agent and a spot of water and stirring, and puts into baking oven for heating to 110 ℃～330 ℃, the CO that utilizes original position to produce then
2Foaming preparation polyimide foam.It is 16kg/m that this method can prepare density
3～96kg/m
3The heat-insulating flame-retardant polyimide foam, defective is that blowing temperature is high, power consumption, cost is high.
US4263410 disclose a kind of with dianhydride and isocyanic ester furfuryl alcohol, SPA, and the condition that exists of stannous octoate prepare the method for polyimide foam material.The foam of this method preparation has better heat-resisting property.But defective is the reaction heat of furfuryl alcohol and SPA can not make the polyimide foam completion of cure, and job efficiency is low.
U.S. Pat 4804504, US4814357, US4855332, US4952611, US5064867 have reported a kind of flexible polyimide foamy preparation method.With the esterification in alcohols (R-OH) solvent of dianhydride or derivatives thereof; Add diamines, pyridine and tensio-active agent and prepare prepolymer solution; Solution is processed powder after drying at a certain temperature, pours into then in the mould and makes the flexible polyimide foam through microwave radiation, high temperature oven heating.The foam flexibility of this method preparation is good, and percentage of open area is high, but defective is a complex process, and cost is high.
WO2004072032A2, U.S. Pat 6956066B2, US7541388, US2006063848, US20040249002, and Chinese patent CN101402743A disclose and a kind of dianhydride and verivate thereof be dissolved in the polar solvent, add preparation foam precursors solution such as whipping agent, catalyzer, tensio-active agent, fire retardant; Then with precursor solution and isocyanic ester through mixing, foam, solidify the method that obtains the polyimide foam material.The polyimide foam over-all properties of this method preparation is better, in the curing molding process, is out of shape seriously but defective is a foam, and shrinking percentage is big, causes utilization rate of raw materials low.
Chinese patent CN101407594A discloses and a kind of dianhydride, the siloxanes that contains active end group, low mass molecule alcohol, catalyzer and tensio-active agent has been formed foam precursors solution in polar solvent; Then solution is mixed with isocyanic ester in proportion, obtain the method for polyimide foam material through foaming, curing.This method has been incorporated into the soft segment of siloxanes on the polyimide stiff molecule main chain, has improved the kindliness of molecular chain, thereby the foamy processing characteristics is increased substantially.But the defective of this method is that foam shrinking percentage in the curing molding process is big, and the material effective rate of utilization is low.
At present, light flexible polyimide foam material mainly adopts liquid phase foaming preparation, and it forms experience foaming process and two stages of solidification process of needing.Because foam structure is in that to solidify the starting stage unstable or insecure, cell wall intensity a little less than, and the further volatilization of residual solvent and whipping agent makes the increase of abscess pressure reduction; Foams then shrink under differential pressure action; Be that moulding is shunk, can reach more than 30% when serious, cause that scrap rate is high, waste of material is serious; Cost is high, has satisfied not the requirement of each high-technology field to its dimensional stability.Therefore, develop low contraction, high-dimensional stability, lightweight, flexible polyimide foam materials, make it both can do the use of high temperature sound-absorbing material, also can do the sandwich material use of low contraction high-dimensional stability is the bottleneck technical problem of being badly in need of solution.
To above defective; The present invention is based on the structure design of staple and the design of components of material; Through adopting triamine and dianhydride and/or acid esters pre-polymerization in polar solvent to obtain ultrabranching polyamide acid prepolymer; Give later stage synthetic foam precursors solution certain rigid, part has improved the frame strength of bubble wall; Foam precursors solution and isocyanic ester mixed foaming obtain containing the rigid structure of imide ring; The frame strength and the rigidity of bubble wall have further been improved; Effectively offset foams owing to the foams that solvent evaporates and imidization cause shrink, finally prepared the low low-cost light flexible polyimide foam material of shrinking.
Summary of the invention
A kind of light flexible polyimide foam material of the present invention and preparation method thereof is characterized in that: be blended in molar ratio by fragrant triamine and aromatic dianhydride and/or aromatic esters that reaction forms the sour prepolymer of ultrabranching polyamide in the polar solvent; Add remaining aromatic dianhydride and/or aromatic esters, catalyzer, tensio-active agent then, reach auxiliary agent formation foam precursors solution; Foam precursors solution and isocyanic ester form foam intermediate at the mould internal reaction; The process microwave radiation is or/and baking oven for heating obtains light flexible polyimide foam material after solidifying.The molecular structure interlude is fragrant triamine and aromatic dianhydride and/or aromatic esters formation hyperbranched a section; Side chain is the crosslinked or/and linearity range of aromatic dianhydride and/or aromatic esters and isocyanic ester formation; Wherein, R is a kind of structural unit in the table 1, and R ' is a kind of structural unit in the table 2.
The structure of table 1.R
The structure of table 2.R '
Each amounts of components is in weight part in the foam precursors solution, and proportioning is following:
100 parts of aromatic dianhydride and/or aromatic esters
1 part～80 parts of fragrance triamines
50 parts～600 parts of polar solvents
0.01 part～10 parts of catalyzer
0.5 part～100 parts in tensio-active agent
0.5 part～75 parts of low mass molecule alcohols
0 part～100 parts of other auxiliary agents
Foam precursors solution and isocyanic ester mass ratio are 1: (0.5～1.5).
The typical operational procedure of preparation light flexible polyimide foam material of the present invention is following:
(1) preparation ultrabranching polyamide acid pre-polymer solution.Under 20 ℃～60 ℃, normal pressure, adopt polar solvent that fragrant triamine is dissolved in prolong is housed, be connected with N
2Dry four-necked bottle in; Magnetic agitation is dissolved it fully; Mol ratio by fragrant triamine and aromatic dianhydride and/or aromatic esters is 1 then: (0.5～2) slowly adds aromatic dianhydride and/or aromatic esters; Obtain ultrabranching polyamide acid pre-polymer solution after 6 hours～14 hours, wherein ultrabranching polyamide acid prepolymer has following structure:
(2) preparation foam precursors solution.With remaining aromatic dianhydride and/or aromatic esters, catalyzer, tensio-active agent, low mass molecule alcohol, and auxiliary agent add in the above-mentioned pre-polymer solution, heated and stirred can obtain foam precursors solution to constant temperature.
(3) preparation foam intermediate.Take by weighing isocyanic ester, foam precursors solution was stirred 0.05 minute～2 minutes with isocyanic ester in proportion fast, the mould internal reaction of pouring preheating into forms foam intermediate, and wherein foam intermediate has following structure:
4) the polyimide foam material of preparation imidization.The foam intermediate room temperature was placed 0.5 hour～12 hours, after the demoulding in the vacuum drying oven of microwave oven and/or 150 ℃～300 ℃ solidifying and setting 0.5 hour～10 hours, obtain the light flexible polyimide foam material of abundant imidization.
Being used for isocyanic ester of the present invention is 4; 4 '-diphenylmethanediisocyanate, tolylene diisocyanate, in phenylene vulcabond, naphthyl vulcabond, hexamethylene vulcabond, poly methylene poly phenyl poly isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or the isoflurane chalcone diisocyanate one or both.
Being used for polar solvent of the present invention is hexamethylphosphoramide, DMAC N,N, N-Methyl pyrrolidone, DMSO 99.8MIN., N-pyridine oxide, N, a kind of in dinethylformamide or the diethylene glycol dimethyl ether.
Being used for catalyzer of the present invention is trolamine, N; N-dimethylethanolamine, N; N '-lutidine, dimethyl benzylamine, N, in N-dimethyl-hexadecylamine, triethylenediamine, N-ethylmorpholine, two (dimethyl amido ethyls) and the triethylamine organic amine catalyzer a kind of respectively with stannous octoate, dibutyl tin laurate, dibutyltin diacetate, dibutyltin sulfide and tetrabutyl tin organo-metallic salt catalyzer in a kind of mixture; Tensio-active agent is a kind of in PEG-12 YSR 3286 (DC-193) and the AK series organic silicone oil.
Be used for low mass molecule alcohol of the present invention and be one or both of methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, octanol, furfuryl alcohol and low-molecular-weight polyethylene glycol.
Being used for auxiliary agent of the present invention is fluoro trichloromethane, 1,1-two chloro-1-fluoroethanes, difluoro monochlorethane, 1,1,1; 3,3-pentafluoropropane, 1,1,1; 3,3-3-pentafluorobutane, 1,1; 1 ,-trichloroethane, 1, one or both in 1-C2H4F2 C2H4F2, Skellysolve A, iso-pentane, pentamethylene, sherwood oil, water, full phosphorus fire retardant such as methyl-phosphoric acid dimethyl ester, halogenated phosphate fire retardant such as the trichlorine propyl phosphate.
Add tensio-active agent in order to the stable foam system in the present invention's prescription; Add entry, amine and metallic salt composite catalyst in order to quicken and the reaction of coordination system; Add frothing aid in order to produce a large amount of gas foamings, so that reduce density of material; Can add full phosphorus fire retardant such as methyl-phosphoric acid dimethyl ester, diethyl ethylphosphate, fire retardants such as halogenated phosphate fire retardant such as trichlorine propyl phosphate, tricresyl phosphate (β-chloroethyl) ester are in order to improve the anti-flame retardant properties of goods of the present invention.
The present invention has following difference and advantage:
(1) the foam contraction rate is merely-35.34%～21.75%, and utilization rate of raw materials is high, and flexible good;
(2) foam density is 6.0kg/m
3～31.0kg/m
3, second-order transition temperature is 235 ℃～320 ℃;
(3) foam aperture is even, and percentage of open area is high, has good sqouynd absorption lowering noise performance and flame retardant properties;
(4) preparation technology is simple, and foam precursors solution stores good stability, moulding process asepsis environment-protecting;
(5) compare with the polyimide foam material of diamine preparation with traditional binary acid anhydride, adopt tertiary amine, the polyimide foam material price of binary acid anhydride and isocyanic ester preparation is cheap;
(6) resulting product stable performance of the present invention, Application Areas is wide.
Embodiment:
Below can further understand the present invention through embodiment, but can not limit content of the present 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
Restrain three (4-aminophenyl) amine solvents in prolong being housed, being connected with N with 210 gram Ns with 3.60
2Dry four-necked bottle in, magnetic agitation is heated to 45 ℃ and keep constant temperature gradually, with 4.96 grams 3,3 ', 4,4 '-UVNUL MS-40 tetracarboxylic acid dianhydride slowly added in the four-necked bottle in 1 hour, was cooled to 25 ℃ after 8 hours, obtained solution I then.Solution I is moved in the beaker, add 0.13 gram trolamine, 0.11 gram dibutyl tin laurate, 0.24 gram deionized water, 1.33 gram DC-193,3.3 gram polyoxyethylene glycol (PEG-600), 1.93 gram anhydrous methanols, and 43.17 other grams 3; 3 ', 4,4 '-UVNUL MS-40 tetracarboxylic acid dianhydride; Stir; Be heated to 145 ℃ gradually, react and reduce to room temperature after 4 hours, can obtain heavy-gravity precursor solution II.
Measure the above-mentioned precursor solution II of 25 grams, stirred 0.05～2 minute fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 1～10 minute with 13 gram poly methylene poly phenyl poly isocyanates; Finalized the design 30～40 minutes putting into microwave equipment after the midbody demoulding then, the midbody that obtains finalizing the design is put into vacuum drying oven with the midbody after the typing, solidifies 1 hour down at 235 ℃, obtains faint yellow solid-state polyimide foam material after the cooling.
Fundamental property through the polyimide foam material of test implementation example 1 preparation is following:
Density 0.020g/cm
3
Shrinking percentage 8.6%
Compression set 6%
303 ℃ of second-order transition temperatures
Embodiment 2
Restrain three (4-aminophenyl) amine solvents in prolong being housed, being connected with N with 2330 gram Ns with 29.91
2Dry four-necked bottle in, magnetic agitation is heated to 45 ℃ and keep constant temperature gradually, with 35.60 grams 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride slowly added in the four-necked bottle in 3.5 hours, was cooled to 25 ℃ after 12 hours, obtained solution I then.Solution I is moved in the beaker, add 0.53 gram trolamine, 0.71 gram dibutyl tin laurate, 2.87 gram deionized waters, 9.38 gram AK-8805,10.65 gram polyoxyethylene glycol (PEG-600), 8.12 gram anhydrous methanols, and 353.06 other grams 3; 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride; Stir; Be heated to 125 ℃ gradually, react and reduce to room temperature after 5 hours, can obtain heavy-gravity precursor solution II.
Measure the above-mentioned precursor solution II of 150 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 3 minutes～10 minutes with 190 gram poly methylene poly phenyl poly isocyanates; Finalized the design 45 minutes～60 minutes putting into microwave equipment after the midbody demoulding then, the midbody that obtains finalizing the design, the midbody of will finalizing the design is put into vacuum drying oven, solidifies 2.5 hours down at 250 ℃, and the cooling back demoulding obtains yellow solid polyimide foam materials.
Fundamental property through the polyimide foam material of test implementation example 2 preparations is following:
Density 0.017g/cm
3
Shrinking percentage 13.8%
Compression set 6%
310 ℃ of second-order transition temperatures
Embodiment 3
With 10.11 grams 1,3,5-three (4-amino-benzene oxygen) benzene is dissolved in prolong is housed, is connected with N with 375 gram N,N-DIMETHYLACETAMIDEs
2Dry four-necked bottle in, magnetic agitation is heated to 40 ℃ and keep constant temperature gradually, with 5.52 grams 1,2,4, the 5-pyromellitic acid anhydride slowly added in the four-necked bottle in 2 hours, was cooled to 25 ℃ after 10 hours, obtained solution I then.Solution I is moved in the beaker, add 0.21 gram trolamine, 0.34 gram dibutyl tin laurate, 1.48 gram deionized waters, 9.76 gram AK-8805,6.77 gram polyoxyethylene glycol (PEG-600), 3.24 gram anhydrous methanols, and 76.34 other grams 1; 2,4, the 5-pyromellitic acid anhydride; Stir; Be heated to 90 ℃ gradually, react and reduce to room temperature after 3.5 hours, can obtain heavy-gravity precursor solution II.
Measure the above-mentioned precursor solution II of 20 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 1 minute～10 minutes with 9 gram poly methylene poly phenyl poly isocyanates and 7 gram isophorone diisocyanates; Finalized the design 30 minutes～45 minutes putting into microwave equipment after the midbody demoulding then, the midbody that obtains finalizing the design, the midbody of will finalizing the design is put into vacuum drying oven, solidifies 2 hours down at 265 ℃, and the cooling back demoulding obtains yellow solid polyimide foam materials.
Fundamental property through the polyimide foam material of test implementation example 3 preparations is following:
Density 0.012g/cm
3
Shrinking percentage 11.4%
Compression set 5%
292 ℃ of second-order transition temperatures
Embodiment 4
At logical N
2Dry four-necked bottle in, with 3.64 the gram 3,3 ', 4,4 '-UVNUL MS-40 tetracarboxylic acid dianhydride, 2.46 the gram 1; 2,4,5-pyromellitic acid anhydride and 4.51 grams 1,3,5-three (4-amino-benzene oxygen) benzene are invested in the 262.42 gram N,N-DIMETHYLACETAMIDEs; Solution is warming up to 45 ℃, stirs, and treats 3,3 ', 4; 4 '-UVNUL MS-40 tetracarboxylic acid dianhydride, 1,2,4,5-pyromellitic acid anhydride and 1; 3, after 5-three (4-amino-benzene oxygen) benzene fully reacts 12 hours, obtain solution I, reduce to 25 ℃ then; Add 0.05 gram triethylene diamine, 0.07 gram stannous octoate, 12.01 gram deionized waters, 32.01 gram DC-193,7.56 gram polyoxyethylene glycol, 2.35 gram anhydrous methanols, and 31.85 other grams 1,2,4; The 5-pyromellitic acid anhydride is heated to 120 ℃ and stir gradually, reduces to 45 ℃ then, can obtain thickness precursor solution II.
Measure the above-mentioned precursor solution of 20 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 1 minute～10 minutes with 13 gram poly methylene poly phenyl poly isocyanates; The midbody room temperature was placed 60 minutes, put into vacuum drying oven after the demoulding, solidified 2 hours down, obtain yellow solid polyimide foam materials after the cooling at 240 ℃.
Fundamental property through the polyimide foam material of test implementation example 4 preparations is following:
Density 0.022g/cm
3
Shrinking percentage 6.8%
Compression set 5.5%
285 ℃ of second-order transition temperatures
Embodiment 5
Measure the solution I in the 30 gram embodiments 1, add 0.13 gram trolamine, 0.11 gram stannous octoate, 1.25 gram deionized waters, 1.76 gram DC-193,3.3 gram polyoxyethylene glycol (PEG-600), 1.93 gram anhydrous methanols, 5 grams 1; 1-two chloro-1-fluoroethanes and 43.17 other grams 3,3 ', 4; 4 '-UVNUL MS-40 tetracarboxylic acid dianhydride stirs, and is heated to 145 ℃ gradually; React and reduce to room temperature after 4 hours, can obtain heavy-gravity precursor solution II.
Measure the above-mentioned precursor solution II of 35 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 2 minutes～10 minutes with 35 gram poly methylene poly phenyl poly isocyanates; The midbody room temperature was placed 40 minutes, put into vacuum drying oven after the demoulding, solidified 2 hours down at 280 ℃, the cooling back demoulding obtains yellow solid polyimide foam materials.
Fundamental property through the polyimide foam material of test implementation example 5 preparations is following:
Density 0.015g/cm
3
Shrinking percentage 3.7%
Compression set 6%
297 ℃ of second-order transition temperatures
Embodiment 6
Measure the solution I in the 30 gram embodiments 1, add 0.08 gram triethylene diamine, 0.11 gram stannous octoate, 13 gram deionized waters, 12 gram DC-193,13 gram polyoxyethylene glycol, 11 gram anhydrous methanols, 5 grams 1; 1-two chloro-1-fluoroethanes and 50.19 other grams 3,3 ', 4; 4 '-UVNUL MS-40 tetracarboxylic acid dianhydride stirs, and is heated to 120 ℃ gradually; React and reduce to room temperature after 4 hours, can obtain heavy-gravity precursor solution II.
Measure the above-mentioned precursor solution of 20 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain midbody after 1 minute～10 minutes with 8 gram poly methylene poly phenyl poly isocyanates and 8 gram isophorone diisocyanates; Room temperature was placed after 30 minutes, finalized the design 3 minutes～15 minutes putting into microwave oven after the midbody demoulding, and then put into vacuum drying oven, solidified 1 hour down at 250 ℃, and the cooling back demoulding obtains yellow solid polyimide foam materials.
Fundamental property through the polyimide foam material of test implementation example 6 preparations is following:
Density 0.016g/cm
3
Shrinking percentage-18.4%
Compression set 6%
284 ℃ of second-order transition temperatures
Claims (7)
1. light flexible polyimide foam material; It is characterized in that: the foam precursors solution that ultrabranching polyamide acid copolymer, low mass molecule alcohol, catalyzer, tensio-active agent and the auxiliary agent that said light flexible polyimide foam is formed in polar solvent by fragrant triamine and aromatic dianhydride and/or aromatic esters forms, with isocyanate reaction, solidify a kind of light flexible polyimide foam material that obtains; The interlude of molecular structure is hyperbranched a section that fragrant triamine and aromatic dianhydride and/or aromatic esters form, side chain be aromatic dianhydride and/or aromatic esters with the crosslinked of isocyanic ester formation or/and linearity range,
Wherein, R is a kind of structural unit among
, and R ' is a kind of structural unit among
;
Each amounts of components is in weight part in the foam precursors solution, and proportioning is following:
Foam precursors solution and isocyanic ester mass ratio are 1: (0.5～1.5).
2. the said light flexible polyimide foam of claim 1 material, its preparation method is following:
(1) preparation ultrabranching polyamide acid pre-polymer solution under 20 ℃～60 ℃, normal pressure, adopts polar solvent that fragrant triamine is dissolved in prolong is housed, is connected with N
2Dry four-necked bottle in; Magnetic agitation is dissolved it fully; Mol ratio by fragrant triamine and aromatic dianhydride and/or aromatic esters is 1 then: (0.5～2) slowly adds aromatic dianhydride and/or aromatic esters; Obtain ultrabranching polyamide acid pre-polymer solution after 6 hours～14 hours, wherein ultrabranching polyamide acid prepolymer has following structure:
(2) preparation foam precursors solution, with remaining aromatic dianhydride and/or aromatic esters, catalyzer, tensio-active agent, low mass molecule alcohol, and auxiliary agent add in the above-mentioned pre-polymer solution, heated and stirred can obtain foam precursors solution to constant temperature;
(3) the preparation foam intermediate takes by weighing isocyanic ester, and foam precursors solution was stirred 0.05 minute～2 minutes with isocyanic ester in proportion fast, and the mould internal reaction of pouring preheating into forms foam intermediate, and wherein foam intermediate has following structure:
(4) the polyimide foam material of preparation imidization; The foam intermediate room temperature was placed 0.5 hour～12 hours; After the demoulding in the vacuum drying oven of microwave oven and/or 150 ℃～300 ℃ solidifying and setting 0.5 hour～10 hours, obtain the light flexible polyimide foam material of abundant imidization.
3. the said light flexible polyimide foam of claim 1 material; It is characterized in that: isocyanic ester wherein is 4; 4 '-diphenylmethanediisocyanate, tolylene diisocyanate, in phenylene vulcabond, naphthyl vulcabond, hexamethylene vulcabond, poly methylene poly phenyl poly isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or the isoflurane chalcone diisocyanate one or both.
4. the said light flexible polyimide foam of claim 1 material; It is characterized in that: polar solvent wherein is hexamethylphosphoramide, N; N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, DMSO 99.8MIN., N-pyridine oxide, N, a kind of in dinethylformamide or the diethylene glycol dimethyl ether.
5. the said light flexible polyimide foam of claim 1 material; It is characterized in that: catalyzer wherein is trolamine, N; N-dimethylethanolamine, N; N '-lutidine, dimethyl benzylamine, N, in N-dimethyl-hexadecylamine, triethylenediamine, N-ethylmorpholine, two (dimethyl amido ethyls) and the triethylamine organic amine catalyzer a kind of respectively with stannous octoate, dibutyl tin laurate, dibutyltin diacetate, dibutyltin sulfide and tetrabutyl tin organo-metallic salt catalyzer in a kind of mixture; Tensio-active agent is PEG-12, a kind of in YSR 3286 DC-193 and the AK series organic silicone oil.
6. the said light flexible polyimide foam of claim 1 material, it is characterized in that: low mass molecule alcohol wherein is one or both in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, octanol, furfuryl alcohol and the low-molecular-weight polyethylene glycol.
7. the said light flexible polyimide foam of claim 1 material, it is characterized in that: auxiliary agent wherein is a fluoro trichloromethane, 1,1-two chloro-1-fluoroethanes, difluoro monochlorethane, 1,1; 1,3,3-pentafluoropropane, 1,1; 1,3,3-3-pentafluorobutane, 1,1; 1 ,-trichloroethane, 1, one or both in 1-C2H4F2 C2H4F2, Skellysolve A, iso-pentane, pentamethylene, sherwood oil, water, methyl-phosphoric acid dimethyl ester, the trichlorine propyl phosphate.
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| CN103865032B (en) * | 2014-02-25 | 2016-04-06 | 江苏康乐新材料科技有限公司 | Watersoluble closed type polyisocyanate crosslinking agent of highly branched structure and preparation method thereof |
| CN106032433A (en) * | 2015-03-09 | 2016-10-19 | 常州天晟新材料股份有限公司 | Polyimide foamed material and preparation method thereof |
| CN107540839B (en) * | 2016-06-27 | 2021-04-23 | 上海康达化工新材料集团股份有限公司 | Light sound-absorbing heat-insulating polyimide foam material and preparation method thereof |
| CN106188598B (en) * | 2016-08-02 | 2018-11-27 | 南通凯英薄膜技术有限公司 | A kind of flame-resistant high-temperature-resistant polyimides composite plate and preparation method thereof |
| CN106633867A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type 14BDAPB branched polyimide resin thin film and preparation method thereof |
| CN106519682A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106633875A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | HQDA type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN107629208A (en) * | 2017-10-10 | 2018-01-26 | 丁玉琴 | A kind of preparation method of Polyimide foams |
| CN107903430B (en) * | 2017-12-05 | 2020-10-16 | 北京工商大学 | Preparation method of isocyanate-based polyimide rigid foam |
| CN108017786A (en) * | 2017-12-24 | 2018-05-11 | 桂林理工大学 | The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride |
| CN108774143A (en) * | 2018-07-31 | 2018-11-09 | 湖南工业大学 | A kind of Triamine monomer and its preparation method and application centered on naphthalene structure |
| CN110028668B (en) * | 2019-04-25 | 2021-08-10 | 航天材料及工艺研究所 | Preparation method of hard polyimide foam material |
| CN112824438B (en) * | 2019-11-20 | 2022-05-17 | 湘潭大学 | Synthetic method of polyimide |
| CN114854009B (en) * | 2022-05-13 | 2023-05-30 | 华中科技大学 | Polyimide foam and preparation method thereof |
| CN115368735A (en) * | 2022-08-31 | 2022-11-22 | 常州福隆科技新材料有限公司 | Polyimide foam material with hierarchical pore structure and preparation method thereof |
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| CN101812232A (en) * | 2010-04-09 | 2010-08-25 | 北京航空航天大学 | Polyimide foam and preparation method thereof |
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