CN102134396A - Light flexible polyimide foam material and preparation method thereof - Google Patents
Light flexible polyimide foam material and preparation method thereof Download PDFInfo
- Publication number
- CN102134396A CN102134396A CN 201010600260 CN201010600260A CN102134396A CN 102134396 A CN102134396 A CN 102134396A CN 201010600260 CN201010600260 CN 201010600260 CN 201010600260 A CN201010600260 A CN 201010600260A CN 102134396 A CN102134396 A CN 102134396A
- Authority
- CN
- China
- Prior art keywords
- aromatic
- foam
- polyimide foam
- preparation
- light flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a light flexible polyimide foam material and a preparation method thereof. The light flexible polyimide foam material is prepared through the reaction and solidification of the following raw materials: catalytic agents, surface active agents, addition agents, isocyanate and linearpolyamic acid prepolymer formed by aromatic diamine, aromatic dianhydride and/or aromatic acid ester. The middle section of the molecular structure is a linear segment formed by the aromatic diamine, the aromatic dianhydride and/or the aromatic acid ester, and both sides of the middle section of the molecular structure are crosslinking sections or/and linear sections formed by the aromatic dianhydride, and/or the aromatic acid ester and the isocyanate. The preparation process of the polyimide foam material is simple, the shrinkage factor is from minus 50.42 percent to 20.23 percent, the density is from 4.0kg/m3 to 28.0kg/m3, and the glass-transition temperature is from 260 DEG C to 310 DEG C. The light flexible polyimide foam material is the flexible, sound-absorbing, noise-reducing macromolecule foam material, and is mainly applicable to the fields of aerospace, warships 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, and has that excellent heat insulation and acoustic absorption performance, excellent dielectric properties, good gentle elasticity, intensity can design, anti-irradiation, anti-solvent, difficult combustion and a low performance such as be fuming.The performance of polyimide foam material determines it to serve many purposes, 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 by 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 by the microwave foaming technique, and its foaming and imidization speed are fast, the efficient height, 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.Thermoplastic polyimide is melt extruded in 380 ℃～410 ℃ temperature ranges, by adding whipping agent or foaming in the decompression cooling of 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.The esterification in the solution of small molecular alcohol and ether with dianhydride and derivative thereof, in esterification solution, add diamines then and react, obtain polyamic acid prepolymer solution, again by 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 made 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, pulverize after the oven dry, then high temperature preparation polyimide microsphere and polyimide foam down.
CN101456967A makes composite powder by pore-creating agent is joined in the thermoplastic polyimide powder, prepares polyimide porous material then 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 intermediates 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; Intermediate 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 by 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, the scrap rate height.
US3772216 is by 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 the blowing temperature height, the power consumption, the cost height.
US4263410 disclose a kind of with dianhydride and isocyanic ester furfuryl alcohol, strong phosphoric acid, 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.But defective is the reaction heat of furfuryl alcohol and strong phosphoric acid 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 made 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 the percentage of open area height, but defective is a complex process, the cost height.
WO2004072032A2, U.S. Pat 6956066B2, US7541388, US2006063848, US20040249002, and Chinese patent CN101402743A disclose and a kind of dianhydride and derivative 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, is out of shape in the curing molding process 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 solidifying starting stage instability or insecure, cell wall intensity a little less than, and the further volatilization of residual solvent and whipping agent makes abscess pressure reduction increase, foams then shrink under differential pressure action, be that moulding is shunk, can reach more than 30% when serious, cause scrap rate height, waste of material serious, cost is high, does not satisfy 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.
At above defective, the present invention is based on the structure design of main component and the design of components of material, by adopting diamines and dianhydride and/or acid esters pre-polymerization in polar solvent to obtain flexibility thermoplastic prepolymer, later stage synthetic foam precursors solution and isocyanic ester mixed foaming obtain containing the rigid structure of imide ring, in the heat treatment for solidification stage, the interstructural synergy of rigid structure and flexibility is finally prepared the low low-cost light flexible polyimide foam material that shrinks.
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 aromatic diamines and aromatic dianhydride and/or aromatic esters that reaction forms the sour prepolymer of linear polyamidoamine 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, and the process microwave radiation is or/and baking oven for heating obtains light flexible polyimide foam material after solidifying.The molecular structure interlude is the linearity range of aromatic diamines and aromatic dianhydride and/or aromatic esters formation, both sides are 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 as follows:
100 parts of aromatic dianhydride and/or aromatic esters
1 part～80 parts of aromatic diamines
50 parts～600 parts of polar solvents
0.01 part～10 parts of catalyzer
0.5 part～100 parts in tensio-active agent
1 part～65 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 as follows:
(1) preparation polyamide thermoplastic acid pre-polymer solution.Under 20 ℃～50 ℃, normal pressure, in polar solvent, add aromatic diamines, it is dissolved fully, mol ratio by aromatic diamines and aromatic dianhydride and/or aromatic esters is 1 then: (0.5～2) adds aromatic dianhydride and/or aromatic esters, obtain polyamic acid prepolymer solution after 4 hours～10 hours, wherein polyamide thermoplastic 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 fast with isocyanic ester in proportion, the mould internal reaction of pouring preheating into forms intermediate, and wherein foam intermediate has following structure:
(4) the polyimide foam material of the abundant imidization of preparation.The intermediate room temperature was placed 0.5 hour～8 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, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), 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 polydimethylsiloxane (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 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 only is-50.42%～20.23%, the utilization rate of raw materials height, and scrap rate is low;
(2) the foam flexibility is good, and density is 4.0kg/m
3～28.0kg/m
3, second-order transition temperature is 260 ℃～310 ℃;
(3) foam aperture is even, and the percentage of open area height has good sqouynd absorption lowering noise performance and flame retardant properties;
(4) preparation technology is simple, and foam precursors solution stability in storage is good, the moulding process asepsis environment-protecting;
(5) compare with the polyimide foam material of diamine preparation with traditional binary acid anhydride, adopt the polyimide foam material price of diamine, binary acid anhydride and isocyanic ester preparation cheap;
(6) resulting product stable performance of the present invention, Application Areas is wide.
Embodiment:
The present invention can be further understood by the following examples, but content of the present invention can not be limited.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
With 2.40 grams 1,2,4,5-pyromellitic acid anhydride and 2.16 grams 3,4 '-diaminodiphenyl oxide are invested in the 100 gram dimethyl formamides and fully stir, treat 1,2,4,5-pyromellitic acid anhydride and 3, after 4 '-diaminodiphenyl oxide fully reacts, solution becomes light yellow, adds 0.08 gram trolamine, 0.15 gram dibutyl tin laurate, 0.50 gram deionized water, 2.21 gram DC-193,1.21 gram polyoxyethylene glycol (PEG-600), 1.12 gram anhydrous methanol, and 30.51 other grams 1,2,4, the 5-pyromellitic acid anhydride stirs, reduce to room temperature then, can obtain light green heavy-gravity foam precursors solution.
Measure the above-mentioned precursor solution of 25 grams, stirred 0.05 minute～2 minutes fast, treat to pour in the mould of preheating after solution begins to turn white, obtain foam intermediate after 1 minute～10 minutes with 28 gram poly methylene poly phenyl poly isocyanates; Microwave equipment typing 30 minutes～60 minutes will be put into then after the intermediate demoulding, the intermediate that obtains finalizing the design, foam intermediate after the typing is put into vacuum drying oven, solidified 1 hour down, obtain faint yellow solid-state polyimide foam material after the cooling at 185 ℃.
The fundamental property of the polyimide foam material of embodiment 1 preparation is as follows after tested:
Density 0.018g/cm
3
Shrinking percentage 9.3%
Compression set 5%
302 ℃ of second-order transition temperatures
Embodiment 2
With 16.34 grams 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride and 5.87 grams 3,4 '-diaminodiphenyl oxide is invested in the 700 gram N,N-DIMETHYLACETAMIDEs and fully stirs, treat 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride and 3, after 4 '-diaminodiphenyl oxide fully reacted, solution became light green, added 0.28 gram trolamine, 0.35 gram dibutyl tin laurate, 4.21 gram deionized water, 18.65 gram DC-193,12.54 gram polyoxyethylene glycol, 5.65 gram anhydrous methanol, and 468.12 other grams 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, be heated to 70 ℃ gradually, stopped 40 minutes, and reduced to 48 ℃ then, can obtain light green heavy-gravity foam precursors solution.
Measure the above-mentioned precursor solution 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 foam intermediate after 3 minutes～10 minutes with 150 gram poly methylene poly phenyl poly isocyanates; Microwave equipment typing 20 minutes～50 minutes will be put into then after the intermediate demoulding, the intermediate that obtains finalizing the design, foam intermediate after the typing is put into vacuum drying oven, solidified 1.5 hours down, obtain yellow solid polyimide foam materials after the cooling at 176 ℃.
The fundamental property of the polyimide foam material of embodiment 2 preparations is as follows after tested:
Density 0.021g/cm
3
Shrinking percentage 20.8%
Compression set 6%
300 ℃ of second-order transition temperatures
Embodiment 3
With 13.30 grams 1,2,4,5-pyromellitic acid anhydride and 10.63 grams 4,4 '-diaminodiphenyl oxide are invested in the 120 gram N,N-DIMETHYLACETAMIDEs, and solution is warming up to 45 ℃, stir, treat 1,2,4,5-pyromellitic acid anhydride and 4, after 4 '-diaminodiphenyl oxide fully reacted, the solution becomes yellowly was reduced to room temperature then, add 0.38 gram trolamine, 0.16 gram stannous octoate, 9.76 gram deionized water, 12.32 gram DC-193,5.53 gram polyoxyethylene glycol, 5.53 gram anhydrous methanol, and 50 other grams 1,2,4, the 5-pyromellitic acid anhydride, be heated to 115 ℃ and stir gradually, reduce to room temperature then, can obtain blackish green heavy-gravity foam precursors solution.
Measure the above-mentioned precursor solution of 20 grams, stirred 0.05 minute～2 minutes fast with 18 gram poly methylene poly phenyl poly isocyanates and 8 gram isophorone diisocyanates, treat to pour in the mould of preheating after solution begins to turn white, obtain foam intermediate after 1 minute～10 minutes; To put into microwave equipment typing 35 minutes～45 minutes after the intermediate demoulding then, the intermediate that obtains finalizing the design is put into vacuum drying oven with the foam intermediate after the typing, solidifies 2 hours down at 205 ℃, obtains yellow solid polyimide foam materials after the cooling.
The fundamental property of the polyimide foam material of embodiment 3 preparations is as follows after tested:
Density 0.021g/cm
3
Shrinking percentage 20.8%
Compression set 6%
287 ℃ of second-order transition temperatures
Embodiment 4
With 9.65 grams 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 8.68 restrain 1,2,4,5-pyromellitic acid anhydride and 10.74 grams 3,4 '-diaminodiphenyl oxide are invested in the 100 gram N,N-DIMETHYLACETAMIDEs, and solution is warming up to 40 ℃, stir, treat 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 1,2,4,5-pyromellitic acid anhydride and 3, after 4 '-diaminodiphenyl oxide fully reacted, solution became light yellow, reduced to room temperature then, add 0.35 gram triethylene diamine, 0.27 gram stannous octoate, 0.85 gram deionized water, 21.42 gram AK-8805,10.41 gram polyoxyethylene glycol, 3.75 gram anhydrous methanol, and 56.70 other grams 1,2,4, the 5-pyromellitic acid anhydride, be heated to 70 ℃ and stir gradually, reduce to 45 ℃ then, can obtain green heavy-gravity foam precursors solution.
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 foam intermediate after 1 minute～10 minutes with 27 gram poly methylene poly phenyl poly isocyanates; The intermediate room temperature was placed 90 minutes, put into vacuum drying oven after the demoulding, solidified 2 hours down, obtain yellow solid polyimide foam materials after the cooling at 243 ℃.
The fundamental property of the polyimide foam material of embodiment 4 preparations is as follows after tested:
Density 0.024g/cm
3
Shrinking percentage 6.8%
Compression set 5.5%
295 ℃ of second-order transition temperatures
Embodiment 5
With 17.20 grams 1,2,4,5-pyromellitic acid anhydride and 6.56 grams 3,4 '-diaminodiphenyl oxide is invested in the 60 gram N,N-DIMETHYLACETAMIDEs, and solution at room temperature stirs, and treats 1,2,4, after 5-pyromellitic acid anhydride and 3,4 '-diaminodiphenyl oxide fully react, the solution becomes yellowly, add 0.32 gram trimethylene diamines then, 0.43 gram dibutyl tin laurate, 1.35 gram deionized water, 11.23 gram AK-8805,4.41 gram polyoxyethylene glycol, 2.09 the gram anhydrous methanol, 3.56 gram methyl-phosphoric acid dimethyl esters, and 34 other grams 1,2,4, the 5-pyromellitic acid anhydride is heated to 120 ℃ and stir gradually, reduce to room temperature then, can obtain blackish green heavy-gravity foam precursors solution.
Measure the above-mentioned precursor solution 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 foam intermediate after 2 minutes～10 with 35 gram poly methylene poly phenyl poly isocyanates; The intermediate room temperature was placed 120 minutes, put into vacuum drying oven after the demoulding, solidified 2 hours down, obtain yellow solid polyimide foam materials after the cooling at 280 ℃.
The fundamental property of the polyimide foam material of embodiment 5 preparations is as follows after tested:
Density 0.015g/cm
3
Shrinking percentage-23.7%
Compression set 6%
275 ℃ of second-order transition temperatures
Embodiment 6
With 13.01 grams 1,2,4,5-pyromellitic acid anhydride and 10.86 grams 3,4 '-diaminodiphenyl oxide is invested in the 100 gram N,N-DIMETHYLACETAMIDEs, solution is warming up to 40 ℃, stirs, and treats 1,2,4, after 5-pyromellitic acid anhydride and 3,4 '-diaminodiphenyl oxide fully react, the solution becomes yellowly, reduce to room temperature then, add 0.38 gram triethylene diamine, 0.41 gram stannous octoate, 3.24 gram deionized water, 3.32 gram DC-193,6.73 gram polyoxyethylene glycol, 3.74 the gram anhydrous methanol, 5 grams 1,1-two chloro-1-fluoroethanes, and 50 other grams 1,2,4, the 5-pyromellitic acid anhydride, be heated to 110 ℃ and stir gradually, reduce to room temperature then, can obtain blackish green heavy-gravity foam precursors solution.
Measure the above-mentioned precursor solution of 20 grams, stirred 0.05 minute～2 minutes fast with 8 gram poly methylene poly phenyl poly isocyanates and 8 gram isophorone diisocyanates, treat to pour in the mould of preheating after solution begins to turn white, obtain foam intermediate after 1 minute～10 minutes; Room temperature was placed after 30 minutes, will put into microwave oven typing 3 minutes～15 minutes after the intermediate 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.
The fundamental property of the polyimide foam material of embodiment 6 preparations is as follows after tested:
Density 0.016g/cm
3
Shrinking percentage-18.4%
Compression set 6%
289 ℃ of second-order transition temperatures
Claims (7)
1. light flexible polyimide foam material and preparation method thereof, it is characterized in that: the foam precursors solution that linear polyamidoamine acid prepolymer, catalyzer, tensio-active agent and the auxiliary agent that is formed by aromatic diamines and aromatic dianhydride and/or aromatic esters forms, a kind of light flexible polyimide foam material that obtains with isocyanate reaction, curing.The molecular structure interlude is the linearity range of aromatic diamines and aromatic dianhydride and/or aromatic esters formation, both sides are 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 as follows:
100 parts of aromatic dianhydride and/or aromatic esters
1 part～80 parts of aromatic diamines
50 parts～600 parts of polar solvents
0.01 part～10 parts of catalyzer
0.5 part～100 parts in tensio-active agent
1 part～65 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).
2. the described light flexible polyimide foam of claim 1 material, its preparation method is as follows:
(1) preparation polyamide thermoplastic acid pre-polymer solution.Under 20 ℃～50 ℃, normal pressure, in polar solvent, add aromatic diamines, it is dissolved fully, mol ratio by aromatic diamines and aromatic dianhydride and/or aromatic esters is 1 then: (0.5～2) adds aromatic dianhydride and/or aromatic esters, obtain polyamic acid prepolymer solution after 4 hours～10 hours, wherein polyamide thermoplastic 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 fast with isocyanic ester in proportion, the mould internal reaction of pouring preheating into forms intermediate, and wherein foam intermediate has following structure:
(4) the polyimide foam material of the abundant imidization of preparation.The intermediate room temperature was placed 0.5 hour～8 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 described 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 described 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, dimethyl sulfoxide (DMSO), N-pyridine oxide, N, a kind of in dinethylformamide or the diethylene glycol dimethyl ether.
5. the described light flexible polyimide foam of claim 1 material, it is characterized in that: catalyzer wherein is trolamine, N, N-Mono Methyl Ethanol Amine, 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 polydimethylsiloxane (DC-193) and the AK series organic silicone oil.
6. the described 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 and the low-molecular-weight polyethylene glycol.
7. the described 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, full phosphorus fire retardant such as methyl-phosphoric acid dimethyl ester, halogenated phosphate fire retardant such as the trichlorine propyl phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010600260 CN102134396A (en) | 2010-12-22 | 2010-12-22 | Light flexible polyimide foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010600260 CN102134396A (en) | 2010-12-22 | 2010-12-22 | Light flexible polyimide foam material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102134396A true CN102134396A (en) | 2011-07-27 |
Family
ID=44294335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010600260 Pending CN102134396A (en) | 2010-12-22 | 2010-12-22 | Light flexible polyimide foam material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102134396A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232599A (en) * | 2013-05-10 | 2013-08-07 | 中国科学院长春应用化学研究所 | Polyimide foam and preparation method thereof |
| CN104497255A (en) * | 2015-01-13 | 2015-04-08 | 哈尔滨工程大学 | One-step high-flame-retardance low-density polyimide foam preparation method |
| CN105121512A (en) * | 2013-04-19 | 2015-12-02 | 索马龙株式会社 | Polyimide copolymer, and production method for same |
| CN105237766A (en) * | 2015-09-25 | 2016-01-13 | 哈尔滨工程大学 | Preparation method of flexible polyimide foam material having regular cell structure |
| CN107474250A (en) * | 2017-09-22 | 2017-12-15 | 长春理工大学 | It is a kind of can multiple melt processing acid imide material and preparation method thereof |
| WO2017214746A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Formulation and preparation process for ultra-light polyurethane resin |
| CN108715636A (en) * | 2018-06-12 | 2018-10-30 | 常州天晟新材料股份有限公司 | A kind of halogen-free flameproof Polyimide foams and preparation method thereof |
| CN111592649A (en) * | 2020-06-12 | 2020-08-28 | 贵州航天天马机电科技有限公司 | Low-thermal-conductivity polyimide foam material and preparation method thereof |
| CN112646225A (en) * | 2019-10-10 | 2021-04-13 | 保定凯博瑞机械制造有限公司 | Preparation method of flexible open-cell polyimide foam |
| CN112694615A (en) * | 2020-12-30 | 2021-04-23 | 青岛海洋新材料科技有限公司 | Polyimide soft low-density sound absorption foam and preparation method thereof |
| CN115850782A (en) * | 2022-11-25 | 2023-03-28 | 自贡中天胜新材料科技有限公司 | High-strength high-toughness self-curing polyimide foam and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6956066B2 (en) * | 2003-02-11 | 2005-10-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyimide foams |
| CN101501093A (en) * | 2006-10-24 | 2009-08-05 | 新田株式会社 | Polyimide resin |
-
2010
- 2010-12-22 CN CN 201010600260 patent/CN102134396A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6956066B2 (en) * | 2003-02-11 | 2005-10-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyimide foams |
| CN101501093A (en) * | 2006-10-24 | 2009-08-05 | 新田株式会社 | Polyimide resin |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9975998B2 (en) | 2013-04-19 | 2018-05-22 | Somar Corporation | Polyimide copolymer, and production method for same |
| CN105121512A (en) * | 2013-04-19 | 2015-12-02 | 索马龙株式会社 | Polyimide copolymer, and production method for same |
| CN103232599A (en) * | 2013-05-10 | 2013-08-07 | 中国科学院长春应用化学研究所 | Polyimide foam and preparation method thereof |
| CN104497255A (en) * | 2015-01-13 | 2015-04-08 | 哈尔滨工程大学 | One-step high-flame-retardance low-density polyimide foam preparation method |
| CN105237766A (en) * | 2015-09-25 | 2016-01-13 | 哈尔滨工程大学 | Preparation method of flexible polyimide foam material having regular cell structure |
| WO2017214746A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Formulation and preparation process for ultra-light polyurethane resin |
| CN107474250A (en) * | 2017-09-22 | 2017-12-15 | 长春理工大学 | It is a kind of can multiple melt processing acid imide material and preparation method thereof |
| CN107474250B (en) * | 2017-09-22 | 2020-07-03 | 长春理工大学 | Imide material capable of being melt-processed repeatedly and preparation method thereof |
| CN108715636A (en) * | 2018-06-12 | 2018-10-30 | 常州天晟新材料股份有限公司 | A kind of halogen-free flameproof Polyimide foams and preparation method thereof |
| CN108715636B (en) * | 2018-06-12 | 2021-07-27 | 常州天晟新材料股份有限公司 | Halogen-free flame-retardant polyimide foam material and preparation method thereof |
| CN112646225A (en) * | 2019-10-10 | 2021-04-13 | 保定凯博瑞机械制造有限公司 | Preparation method of flexible open-cell polyimide foam |
| CN111592649A (en) * | 2020-06-12 | 2020-08-28 | 贵州航天天马机电科技有限公司 | Low-thermal-conductivity polyimide foam material and preparation method thereof |
| CN112694615A (en) * | 2020-12-30 | 2021-04-23 | 青岛海洋新材料科技有限公司 | Polyimide soft low-density sound absorption foam and preparation method thereof |
| CN115850782A (en) * | 2022-11-25 | 2023-03-28 | 自贡中天胜新材料科技有限公司 | High-strength high-toughness self-curing polyimide foam and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093714B (en) | Light flexible polymide foam material and preparation method thereof | |
| CN102134395B (en) | Modified light flexible polyimide foam material and preparation method thereof | |
| CN102134396A (en) | Light flexible polyimide foam material and preparation method thereof | |
| CN101812232B (en) | Polyimide foam and preparation method thereof | |
| CN101402743B (en) | Polyimide foam and method of producing the same | |
| CN107540839B (en) | Light sound-absorbing heat-insulating polyimide foam material and preparation method thereof | |
| CN101407594B (en) | Modified polyimides foam and preparation thereof | |
| US7541388B2 (en) | Polyimide foams | |
| CN103275319B (en) | Polyimide foam and preparation method thereof | |
| EP1167427B1 (en) | Aromatic polyimide foam | |
| CN102964834B (en) | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof | |
| WO2015180063A1 (en) | Method for continuously preparing solvent-free open-cell and closed-cell polyimide foam | |
| CN101113209B (en) | Polysiloxane acid imide foam and method for preparing same | |
| CN110655790A (en) | Production method of polyimide foam material | |
| CN111793237B (en) | Production method of rigid polyimide foam material | |
| CN104829835B (en) | Preparation method of isocyanate-based polyimide foam | |
| CN103897395A (en) | Preparation method of hydrotalcite and polyimide composite foam material | |
| CN103232599A (en) | Polyimide foam and preparation method thereof | |
| CN106589373A (en) | Super-hydrophobic polyimide foam and production method thereof | |
| CN104497255A (en) | One-step high-flame-retardance low-density polyimide foam preparation method | |
| KR100259489B1 (en) | Preparation for polyimide foam | |
| CN102850569B (en) | Preparation method of polyimide foam | |
| CN105315464B (en) | Prepare the method with regular three-dimensional dimension polyimide foam | |
| CN115010925B (en) | Polyimide foam material with interlocking double-network structure, and preparation method and application thereof | |
| CN114395158B (en) | Preparation method of low-density, high-temperature-resistant and high-uniformity closed-cell rigid polyimide foam material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110727 |