CN106032433A - Polyimide foamed material and preparation method thereof - Google Patents
Polyimide foamed material and preparation method thereof Download PDFInfo
- Publication number
- CN106032433A CN106032433A CN201510103241.3A CN201510103241A CN106032433A CN 106032433 A CN106032433 A CN 106032433A CN 201510103241 A CN201510103241 A CN 201510103241A CN 106032433 A CN106032433 A CN 106032433A
- Authority
- CN
- China
- Prior art keywords
- solution
- dianhydride
- foams
- parts
- polyimide
- 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
Abstract
The invention belongs to the field of new materials, and specifically relates to a polyimide foamed material and a preparation method thereof. The polyimide foamed material comprises the following components in percentage by weight: 10 to 70% of dianhydride, 4 to 20% of foaming agent, 10 to 40% of polar solvent, 0.1 to 8% of catalyst, 2 to 20% of surfactant, and 5 to 70% of isocyanate. The preparation method comprises the following steps: dissolving dianhydride into a polar solvent, adding part of foaming agent, then adding a certain amount of surfactant, catalyst, and flame retardant, and residual foaming agent, finally adding isocyanate, and carrying out a foaming treatment. The preparation technology is simple, the process is easy to control, and the produced foamed material has an excellent heatproof and sound absorbing performance.
Description
Technical field
The invention belongs to field of new, be specifically related to a kind of Polyimide foams and system thereof
Preparation Method.
Background technology
Polyimide foam has many good characteristics in application aspect.Low-density polyimide
Foam is mainly used in heat insulation and acoustic absorption field.China in Recent Years grinds at low-density polyimide foam
More work is had on studying carefully, but its work mostly complex process, product density is the lowest, or produces
Product thermostability is bad.
Summary of the invention
Invention broadly provides a kind of Polyimide foams and preparation method thereof, one-step method
Preparing Polyimide foams, preparation technology is simple, and process is easy to control, the foam material prepared
Material heat resistance, sound absorption qualities are good.Its technical scheme is as follows:
A kind of Polyimide foams, its raw material includes following weight percents:
Described Polyimide foams also includes the fire retardant that percentage by weight is 4～20%.
Described dianhydride is aromatic dianhydride.
The percentage by weight of described aromatic dianhydride is 30～60%, the percentage by weight of isocyanates
It is 10～50%.
Described aromatic dianhydride be pyromellitic acid anhydride, 3,3 ' 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA),
3,3 ' 4,4 '-diphenyl thio-ether tetrformate dianhydride, 4,4 '-diphenyl ether dianhydride, 2,3,3', 4'-diphenyl ether
Tetracarboxylic acid dianhydride, 3,3 ' 4,4 '-biphenyl dianhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and
One or more in 3,3', 4,4'-triphen bis ether tetracarboxylic acid dianhydride；
Described foaming agent is water, methanol, ethanol, acetone, ethylene glycol monobutyl ether, ethylene glycol fourth
One in ether, ethylene glycol-600, Chlorofluorocarbons (CFCs), hydrogen fluorohydrocarbon, triethylamine and oxolane or
Several；
Described polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-first
One or more in base ketopyrrolidine；
Described catalyst is one or more in amines catalyst and/or metallic catalyst；
Described surfactant is siloxane type surfactants；
Described isocyanates is aromatic isocyanate and/or aliphatic isocyanates and/or aromatic ester
One or more in kind isocyanate.
Described siloxane type surfactants is polyether modified silicon oil, polyether modified siloxane, water
Dissolubility silicone oil, silicone, silicone glycol copolymer and organic silicon polyether copolymer surface activity
One or more in agent；
Described isocyanates is methyl diphenylene diisocyanate, methyl diisocyanate, many benzene
Quito methylene polyisocyanates, poly aromatic isocyanate, modified diphenylmethane two are different
Cyanate, hexamethylene diisocyanate, isofoer diisocyanate and phenylenedimethylidyne two
One or more in isocyanates.
The preparation method of a kind of Polyimide foams, comprises the following steps:
(1) dianhydride taking 10～70 weight portions is dissolved in the polar solvent of 10～40 weight portions；
(2) in the solution that step (1) prepares, add partial foaming agent, obtain the first solution；
(3) surfactant of 2～20 weight portions, 0.1～8 catalyst, 4～20 of weight portion are taken
The fire retardant of weight portion and residue foaming agent mix homogeneously, obtain the second solution；
(4) by the first solution and the second solution mix homogeneously；
(5) take in the mixed liquor of isocyanates addition step (4) gained of 5～70 weight portions,
Carry out mixed at high speed process；
(6) rapid being poured into by the mixed liquor of step (5) gained in the container for foaming carries out sending out
Bubble processes, and then carries out microwave radiation processing or heat treatment, i.e. prepares described polyimide foam
Material.
Wherein, the rotating speed carrying out mixed at high speed process described in step (5) is 800～4500rpm.
The power carrying out microwave radiation processing described in step (6) is 0.1～0.5kw/kg foam,
The temperature carrying out heat treatment is 150～250 DEG C.
Described step (1) is specially and the dianhydride of formula ratio is joined temperature is 90～130 DEG C
In the polar solvent of formula ratio, constant temperature stirring makes dianhydride dissolve, and is then cooled to by solution
70～85 DEG C；
Described step (2) is specially and adds in the solution that step (1) prepares by partial foaming agent,
After stirring and dissolving, solution is cooled to 30～50 DEG C；
It is 5～20S that described step (5) is specially the incorporation time of the first solution and the second solution.
Described step (6) is specially to be poured into rapidly for foaming by the mixed liquor of step (5) gained
Container in foam, when foam surface is the most tacky, and epidermis is hardening, it is carried out microwave
Radiation treatment or carry out heat treatment, foams gradually become glassy yellow, show that foams are the completeest
Full imidization, prepares described Polyimide foams.
Using above-mentioned Polyimide foams and preparation method thereof, the present invention has following excellent
Point:
(1) this invention directly uses aromatic dianhydride and isocyanates mixed at high speed, through making
Make polyreaction and foaming carry out with suitable catalyst, foaming agent and other additives simultaneously,
One-step method prepares polyimide foam.This invention raw material and technique are simple, and process is easy to control,
In whole preparation process, refuse is less, thus the productivity of foam is significantly higher.Finally, either
Using opening or closed die, this technique is closeer than conventional technique can better control over foam
Degree；
(2) without external energy when the present invention foams, there is wider range of application；
(3) foam density of the present invention is at about 10kg/m3, and foam mostly is open celled foam and crosslinking
Structure, average sound absorption coefficient 0.65, and show prominent compression resilience, there is excellence
Machinery, sound absorption, the performance such as heat insulation, high temperature resistant and fire-retardant, so the type foam is suitable as
Sound absorption and heat-barrier material, at vessel, vehicle, building and aerospace field have well application
Prospect.
Detailed description of the invention
The Polyimide foams of the present invention by weight percentage, including:
Wherein, described dianhydride is aromatic dianhydride, described aromatic dianhydride be pyromellitic acid anhydride,
3,3 ' 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ' 4,4 '-diphenyl thio-ether tetrformate dianhydride, 4,
4 '-diphenyl ether dianhydride, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3 ' 4,4 '-biphenyl dianhydride,
One in 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and 3,3', 4,4'-triphen bis ether tetracarboxylic acid dianhydride
Or it is several；
Described foaming agent is water, methanol, ethanol, acetone, ethylene glycol monobutyl ether, ethylene glycol fourth
One in ether, ethylene glycol-600, Chlorofluorocarbons (CFCs), hydrogen fluorohydrocarbon, triethylamine and oxolane or
Several；
Described polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-first
One or more in base ketopyrrolidine；
Described catalyst is one or more in amines catalyst and/or metallic catalyst.Example
As, amines catalyst has33、5、
BL22、LV33、18 and the limited public affairs of air chemical products
Department8154, O Si Specialities, the amines catalyst of Inc company
A-33 etc.；Metallic catalyst is had time gasification chemical product company limitedK-15 etc..
Described surfactant is siloxane type surfactants, described type siloxane surface activity
Agent is polyether modified silicon oil, polyether modified siloxane, water-soluble silicon oil, silicone, silicone second
One or more in diol copolymer and organic silicon polyether copolymer surfactants.Such as,
DC193, DC-195, DC-197, DC-500, DC5598 of Daukangnin GmbH,
The DABCO DC198 of air chemical products company limited, DC4000, DC5000,
DC5143, DC6154, O Si Specialities companyL-620 andSurfactant, andB8433、
BB8465, BB8481, B8487, B8513 etc..
Described isocyanates is aromatic isocyanate and/or aliphatic isocyanates and/or aromatic ester
One or more in kind isocyanate.Such as, methyl diphenylene diisocyanate (MDI),
Methyl diisocyanate (TDI), polyphenyl polymethylene polyisocyanates, many polyaromatic
Isocyanates (PMDI), modified MDI, hexamethylene diisocyanate (HDI), different
Fu Er ketone diisocyanate (IPDI), XDI, the also graceful public affairs of Hensel
DepartmentM、TDI、94 and27
Deng.
Described fire retardant is80 HesOne in 82 or two
Kind.
The preparation method of the Polyimide foams of the present invention comprises the following steps:
(1) taking the dianhydride of 10～70 weight portions and joining temperature is that 90～130 DEG C of weight portions are
In the polar solvent of 10～40, constant temperature stirring makes dianhydride dissolve, and is then cooled to by solution
70～85 DEG C；
(2) partial foaming agent is added in the solution that step (1) prepares, stir and molten
Xie Hou, is cooled to 30～50 DEG C by solution, obtains the first solution；
(3) surfactant of 2～20 weight portions, 0.1～8 catalyst, 4～20 of weight portion are taken
The fire retardant of weight portion and residue foaming agent mix homogeneously, obtain the second solution；
(4) by the first solution and the second solution mix homogeneously；
(5) take in the mixed liquor of isocyanates addition step (4) gained of 5～70 weight portions,
Carrying out mixed at high speed process, rotating speed is 800～4500rpm, and incorporation time is 5～20S；
(6) rapidly the mixed liquor of step (5) gained is poured into foaming in the container for foaming,
When foam surface is the most tacky, and epidermis is hardening, it is carried out microwave radiation processing, carry out
The power of microwave radiation processing is 0.1～0.5kw/kg foam, or carries out heat treatment, carries out heat
The temperature processed is 150～250 DEG C, and foams gradually become glassy yellow, show that foams are
Through complete imidization, prepare described Polyimide foams.
Embodiment 1
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 10 parts of pyromellitic acid anhydrides and be dissolved into N, the N-dimethyl that 13 parts of temperature are 99 DEG C
In formamide solution, continue stirring at this temperature until pyromellitic acid anhydride is completely dissolved.
Then solution is cooled to 79 DEG C.1 part of water and 1 part of methanol, stirring is added after solution cooling
Uniformly, this is a slight exothermic reaction so that the temperature of solution rises about 14 DEG C.Will
Solution is cooled to 49 DEG C, obtains the first solution.Take 0.5 part of DC193,0.5 part of DABCO
DC198,0.5 partL-620,0.5 part1 partWith the mixing of 2 parts of acetone, under room temperature, stirring makes mix homogeneously, obtains the
Two solution.Second solution is poured in the first solution, mix homogeneously, keep the temperature at 38 DEG C.
Take 70 parts of methyl diphenylene diisocyanates and add in above-mentioned prepared mixed solution, at rotating speed
For quickly stirring 10S under the speed conditions of 800rpm, stirring liquid is poured into be available for foaming rapidly
Resistance to hot plate in foam.After 10min, when foam surface is the most tacky, and epidermis is hardening,
Put it into operation 9min, foams in the microwave oven that rated power is 0.1kw/kg foam
Gradually become glassy yellow, show foams imidization completely, i.e. prepare described polyimides
Foamed materials.
Embodiment 2
1, Polyimide foams is configured according to the following ratio
2, preparation method
Taking 10 part 4,4 '-diphenyl ether dianhydride is dissolved into 10 parts of N, N-dimethyl methyls that temperature is 100 DEG C
In the mixed solution of amide, 10 parts of N,N-dimethylacetamide and 9 parts of N-Methyl pyrrolidone,
Continue stirring at this temperature until solid is completely dissolved.Then solution is cooled to 75 DEG C.
Adding 2 parts of Chlorofluorocarbons (CFCs) after solution cooling, stir, this is a slight exothermic reaction,
The temperature making solution rises about 10 DEG C.Solution is cooled to 45 DEG C, obtains the first solution.
Take 1.5 parts of DC6154,1.5 parts of B8513,1.5 parts1.5 parts of DABCO
DC198,1 part of DC-197,9.1 partsK-15 and 2 parts of Chlorofluorocarbons (CFCs), 1 part
Hydrogen fluorohydrocarbon mixes, and under room temperature, stirring makes mix homogeneously, obtains the second solution.Second solution is fallen
Enter in the first solution, mix homogeneously, keep the temperature at 45 DEG C.Take 19.9 parts of modified MDI
Add in above-mentioned prepared mixed solution with 20 parts of XDIs, at rotating speed
For quickly stirring 12S under the speed conditions of 1500rpm, stirring liquid is poured into be available for foaming rapidly
Resistance to hot plate in foam.After 10min, when foam surface is the most tacky, and epidermis is hardening,
Put it into operation 8min, foams in the microwave oven that rated power is 0.2kw/kg foam
Gradually become glassy yellow, show foams imidization completely, i.e. prepare described polyimides
Foamed materials.
Embodiment 3
1, Polyimide foams is configured according to the following ratio
2, preparation method
Taking 20 part 4,4 '-diphenyl ether dianhydride and 10 part 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids are molten
Solution to 10 parts temperature is in the N-Methyl pyrrolidone solution of 130 DEG C, continues at this temperature
Stirring is until 4, and 4 '-diphenyl ether dianhydride and 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids are completely dissolved.
Then solution is cooled to 70 DEG C.Adding 3 parts of water after solution cooling, stir, this is
One slight exothermic reaction so that the temperature of solution rises about 8 DEG C.Solution is cooled to
30 DEG C, obtain the first solution.Take 2 parts of DC-500,2 parts of DC5000,1 part
8154,2 parts5,20 parts82 and 4 parts of water mixing, room
The lower stirring of temperature makes mix homogeneously, obtains the second solution.Second solution is poured in the first solution,
Mix homogeneously, keeps the temperature at 30 DEG C.Take 6 parts of polyphenyl polymethylene polyisocyanates,
6 parts of modified MDI, 6 partsM and 8 parts94 add above-mentioned preparing
Mixed solution in, under the speed conditions that rotating speed is 4500rpm, quickly stir 5S, rapidly
Stirring liquid is poured into and is available in the resistance to hot plate of foaming foaming.After 10min, when foam surface not
The most tacky, when epidermis is hardening, puts it into the microwave that rated power is 0.15kw/kg foam and dry
Running 11min in case, foams gradually become glassy yellow, show foams imines completely
Change, i.e. prepare described Polyimide foams.
Embodiment 4
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 20 parts of 3,3', 4,4'-triphen bis ether tetracarboxylic acid dianhydrides, 20 parts of 3,3', 4'-diphenyl ether tetramethyls
Acid and 30 part 3,3 ' 4,4 '-diphenyl thio-ether tetrformate dianhydride is dissolved into 5 parts that temperature is 90 DEG C
In the mixed solution of DMF and 6 parts of N,N-dimethylacetamide, temperature at this
Degree is lower continues stirring until solid is completely dissolved.Then solution is cooled to 85 DEG C.Solution is cold
Adding 1 part of ethylene glycol monobutyl ether and 2 parts of hydrogen fluorohydrocarbon mixing the most afterwards, stir, this is one
Slight exothermic reaction so that the temperature of solution rises about 12 DEG C.Solution is cooled to 50 DEG C,
Obtain the first solution.Take 3 parts1 partA-33,4 parts82,2 parts of ethylene glycol monobutyl ethers, 1 part of hydrogen fluorohydrocarbon mixing, under room temperature, stirring makes
Mix homogeneously, obtains the second solution.Second solution is poured in the first solution, mix homogeneously,
Keep the temperature at 50 DEG C.Take 2 parts of poly aromatic isocyanates, 2 parts of hexa-methylenes two different
Cyanate and 1 part of XDI add in above-mentioned prepared mixed solution,
Rotating speed be 2000rpm speed conditions under quickly stir 8S, stirring liquid is poured into be available for rapidly
The resistance to hot plate of foaming foams.After 8min, when foam surface is the most tacky, and epidermis is hardening
Time, putting it into temperature is 150 DEG C add to add in hot tank and hanker 10min, and foams gradually become
For glassy yellow, show foams imidization completely, i.e. prepare described polyimide foam material
Material.
Embodiment 5
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 10 part 3,3 ' 4,4 '-biphenyl dianhydride, 5 parts of pyromellitic acid anhydrides are dissolved into temperature
The mixing being 7 parts of N,N-dimethylformamides of 120 DEG C and 8 parts of N-Methyl pyrrolidone is molten
In liquid, continue stirring at this temperature until solid is completely dissolved.Then solution is cooled to
80℃.Being added thereto to 2 parts of oxolane mixing after solution cooling, stir, this is one
Individual slight exothermic reaction so that the temperature of solution rises about 10 DEG C.Solution is cooled to
50 DEG C, obtain the first solution.Take 3 parts of BB8481,3 parts of B8487,1.5 parts
K-15,1.5 parts8154,3 parts80,4 parts
82 and 2 parts of ethanol mixing, under room temperature, stirring makes mix homogeneously, obtains the second solution.By
Two solution are poured in the first solution, and mix homogeneously keeps the temperature at 50 DEG C.Take 25 parts different
Fu Er ketone diisocyanate and 25 partsIt is molten that TDI adds above-mentioned prepared mixing
In liquid, under the speed conditions that rotating speed is 2500rpm, quickly stir 10S, liquid will be stirred rapidly
Pour into and be available in the resistance to hot plate of foaming foaming.After 10min, when foam surface is the most tacky,
When epidermis is hardening, puts it in the microwave oven that rated power is 0.1kw/kg foam and run
10min, foams gradually become glassy yellow, show foams imidization completely, i.e. make
Obtain described Polyimide foams.
Embodiment 6
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 10 part 3,3 ' 4,4 '-biphenyl dianhydride, 10 part 3,3 ' 4,4 '-benzophenone tetracarboxylic two
Acid anhydride, 20 part 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and 20 part 4,4 '-diphenyl ether dianhydride dissolve
To 5 parts of DMAC N,N' dimethyl acetamides that temperature is 100 DEG C and 5 parts of N-Methyl pyrrolidone
In mixed solution, continue stirring at this temperature until solid is completely dissolved.Then solution is cold
But to 70 DEG C.Add 1 part of triethylamine and 1 part of ethylene glycol-600 after solution cooling, stir,
This is a slight exothermic reaction so that the temperature of solution rises about 15 DEG C.Solution is cold
But to 40 DEG C, the first solution is obtained.Take 10 parts of B8513,2 partsLV33、
4 parts82,1 part of methanol and 1 part of ethylene glycol monobutyl ether mixing, under room temperature, stirring makes
Mix homogeneously, obtains the second solution.Second solution is poured in the first solution, mix homogeneously,
Keep the temperature at 40 DEG C.Take 10 parts27 add in above-mentioned prepared mixed solution,
Quickly stirring 7S under the speed conditions that rotating speed is 3000rpm, being poured into by stirring liquid rapidly can
For the resistance to hot plate of foaming foams.After 10min, when foam surface is the most tacky, epidermis becomes
Time hard, putting it into temperature is 250 DEG C add to heat 9min in hot tank, and foams gradually become
Glassy yellow, shows foams imidization completely, i.e. prepares described Polyimide foams.
Embodiment 7
1, Polyimide foam composite material is configured according to the following ratio
2, preparation method
Take 10 parts of pyromellitic acid anhydrides, 10 parts of 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and 10
Part 2,3,3', 4'-diphenyl ether tetraformic dianhydride is dissolved into 4 parts of N, N-dimethyl that temperature is 110 DEG C
Methanamide, 6 parts of DMAC N,N' dimethyl acetamides and the mixed solution of 6 parts of N-Methyl pyrrolidone
In, continue stirring at this temperature until solid is completely dissolved.Then solution is cooled to 85 DEG C.
Adding 5 parts of methanol and 2 parts of ethylene glycol-600 after solution cooling, be uniformly mixed, this is one
Individual slight exothermic reaction so that the temperature of solution rises about 14 DEG C.Solution is cooled to
50 DEG C, obtain the first solution.Take 5 parts of DC5598,5 parts of DC5143,3 parts
18,2 parts33,5 parts8154,12 parts80、
1 part of methanol and 4 parts of ethylene glycol-600 mixing, under room temperature, stirring makes mix homogeneously, obtains second
Solution.Second solution is poured in the first solution, mix homogeneously, keep the temperature at 50 DEG C.
Take 10 parts of poly aromatic isocyanates to add in above-mentioned prepared mixed solution, at rotating speed be
Quickly stir 10S under the speed conditions of 4000rpm, stirring liquid is poured into be available for foaming rapidly
Resistance to hot plate foams.After 10min, when foam surface is the most tacky, and epidermis is hardening, will
It puts into temperature is 200 DEG C add to heat 10min in hot tank, and foams gradually become glassy yellow,
Show foams imidization completely, i.e. prepare described Polyimide foam composite material.
Embodiment 8
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 32 part 3,3 ' 4, it is 90 DEG C that 4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved into 15 parts of temperature
N,N-dimethylacetamide solution in, continue at this temperature stirring until 3,3 ' 4,4 '-
Benzophenone tetracarboxylic dianhydride (BTDA) is completely dissolved.Then solution is cooled to 70 DEG C.After solution cooling
Adding 3 parts of butyl glycol ethers, stir, this is a slight exothermic reaction so that molten
The temperature of liquid rises about 10 DEG C.Solution is cooled to 50 DEG C, obtains the first solution.Take 0.5
PartBL22,0.5 part of DC-195,0.5 part of DC-197,0.5 part of DC4000,
0.5 part of B8433,0.5 part of BB8465,4 parts80 and 3 parts of chlorine fluorine
Hydrocarbon mixes, and under room temperature, stirring makes mix homogeneously, obtains the second solution.Second solution is poured into
In one solution, mix homogeneously, keep the temperature at 40 DEG C.Take 40 parts of methyl diisocyanate
Add in above-mentioned prepared mixed solution, under the speed conditions that rotating speed is 1000rpm quickly
Stirring 20S, pours into stirring liquid rapidly and is available in the resistance to hot plate of foaming foaming.After 8min, when
Foam surface is the most tacky, and when epidermis is hardening, putting it into rated power is 0.2kw/kg
Running 10min in the microwave oven of foam, foams gradually become glassy yellow, show foams
Imidization completely, i.e. prepares described Polyimide foams.
Embodiment 9
1, Polyimide foam composite material is configured according to the following ratio
2, preparation method
Take 12 part 3,3 ' 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and 13 part 3,3', 4,4'-triphens
Bis ether tetracarboxylic acid dianhydride is dissolved into the N,N-dimethylformamide solution that 10 parts of temperature are 110 DEG C
In, continue stirring at this temperature until solid is completely dissolved.Then solution is cooled to 70 DEG C.
Adding 5 parts of ethylene glycol monobutyl ethers, 3 parts of water, 8 parts of oxolanes after solution cooling, stirring is all
Even, this is a slight exothermic reaction so that the temperature of solution rises about 14 DEG C.By molten
Liquid is cooled to 35 DEG C, obtains the first solution.Take 3 parts1 part5,2 parts5 parts5 parts2 parts of oxolanes, 5 parts of water and 7 parts of ethanol, under room temperature, stirring makes mixing
Uniformly, the second solution is obtained.Second solution is poured in the first solution, mix homogeneously, make temperature
Degree is maintained at 35 DEG C.Take 19 parts of methyl diisocyanate and add in above-mentioned prepared mixed solution,
Quickly stirring 10S under the speed conditions that rotating speed is 3000rpm, being poured into by stirring liquid rapidly can
For the resistance to hot plate of foaming foams.After 10min, when foam surface is the most tacky, epidermis becomes
Time hard, put it into operation 10min in the microwave oven that rated power is 0.1kw/kg foam,
Foams gradually become glassy yellow, show foams imidization completely, i.e. prepare described poly-
Acid imide foam material.
Embodiment 10
1, Polyimide foam composite material is configured according to the following ratio
2, preparation method
Take 10 part 3,3 ' 4,4 '-biphenyl dianhydride, 9 part 4,4'-(hexafluoro isopropyl alkene) two phthalandiones
It is 100 DEG C that acid anhydride and 5 parts of 3,3', 4,4'-triphen bis ether tetracarboxylic acid dianhydrides are dissolved into 18 parts of temperature
In N,N-dimethylacetamide solution, continue stirring at this temperature until solid is completely dissolved.
Then solution is cooled to 80 DEG C.Adding 6 parts of butyl glycol ethers after solution cooling, stirring is all
Even, this is a slight exothermic reaction so that the temperature of solution rises about 13 DEG C.By molten
Liquid is cooled to 45 DEG C, obtains the first solution.Take 7 parts of DC4000,4 parts of DC5143,1 partBL22,2 parts2 parts2 parts3 parts3 parts2 parts of ethylene glycol
-600 and 3 parts of butyl glycol ether mixing, under room temperature, stirring makes mix homogeneously, obtains the second solution.
Second solution is poured in the first solution, mix homogeneously, keep the temperature at 45 DEG C.Take 10
Part hexamethylene diisocyanate (HDI) and 13 partsAdd above-mentioned prepared mixing
Close in solution, under the speed conditions that rotating speed is 2500rpm, quickly stir 12S, will stir rapidly
Mix liquid and pour foaming in the resistance to hot plate being available for foaming into.After 9min, when foam surface is no longer sent out
Viscous, when epidermis is hardening, put it in the microwave oven that rated power is 0.13kw/kg foam
Running 11min, foams gradually become glassy yellow, show foams imidization completely,
I.e. prepare described Polyimide foams.
Embodiment 11
1, Polyimide foams is configured according to the following ratio
2, preparation method
Take 18 part 3,3 ' 4, it is 120 DEG C that 4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved into 15 parts of temperature
N-Methyl pyrrolidone solution in, continue at this temperature stirring until 3,3 ' 4,4 '-
Benzophenone tetracarboxylic dianhydride (BTDA) is completely dissolved.Then solution is cooled to 85 DEG C.After solution cooling
Adding 2 parts of ethylene glycol-600, stir, this is a slight exothermic reaction so that molten
The temperature of liquid rises about 14 DEG C.Solution is cooled to 38 DEG C, obtains the first solution.Take 3 parts
DC6154,3 parts of B8433,2 parts5,2 parts5
Part5 parts of ethylene glycol-600 mixing, under room temperature, stirring makes mix homogeneously,
To the second solution.Second solution is poured in the first solution, mix homogeneously, keep the temperature at
38℃.Take 10 parts of poly aromatic isocyanates, 10 parts of methyl diphenylene diisocyanates,
10 parts of methyl diisocyanate and 15 partsAdd above-mentioned prepared mixing
In solution, under the speed conditions that rotating speed is 1000rpm, quickly stir 10S, rapidly will stirring
Liquid is poured in the resistance to hot plate being available for foaming and is foamed.After 10min, when foam surface is the most tacky,
When epidermis is hardening, putting it into temperature is 180 DEG C add to heat 10min, foams in hot tank
Gradually become glassy yellow, show foams imidization completely, i.e. prepare described polyimides
Foamed materials.
Performance test and test result
The sample that above-described embodiment 1-11 prepares is measured density, compressive strength, stretching respectively
Intensity, tension fracture elongation rate, oxygen index (OI), vertical combustion residual mass mark, noise reduction coefficient
And heat conductivity, and observe vertical combustion phenomenon, the data recorded are as follows:
The experimental result that the sample that table 1 embodiment 1-11 prepares records
As shown in Table 1, the density of the Polyimide foams prepared by the present invention exists
10kg/m3Left and right, density is low, lighter in weight；Compressive strength is in about 9kPa, stretching
Intensity, at about 71kPa, has the mechanical performance of excellence；Embodiment 3-11 adds resistance
Combustion agent, oxygen index (OI) is about 29%, more than 27%, belongs to nonflammable material, and vertical combustion is residual
Stay mass fraction about 90%, show that foamed materials fire resistance is good；Heat conductivity is 0.05
Left and right, foam insulation performance described in surface is good, insulation material preferably；Noise reduction coefficient
All more than 0.60, it is possible to eliminate major part noise, there is good sound absorbing capabilities.
Polyimide foams prepared by the present invention, without external energy during foaming, has more
Wide range of application.It addition, refuse is less in whole preparation process, thus the productivity of foam is obvious
Higher.
The present invention directly uses aromatic dianhydride and isocyanates mixed at high speed, suitable through using
Catalyst, foaming agent and other additives make polyreaction and foaming carry out simultaneously, one-step method
Prepare polyimide foam.This invention raw material and technique are simple, and process is easy to control.Product is many
For open celled foam and cross-linked structure, there is heat-resisting, good flame resistance and the feature such as density is ultralow,
Sound-absorbing effect is good, and at vessel, vehicle, building and aerospace field have good application prospect.
It will be apparent to those skilled in the art that can technical scheme as described above and structure
Think, make other various corresponding changes and deformation, and all these changes and deformation
Within all should belonging to the protection domain of the claims in the present invention.
Claims (10)
1. a Polyimide foams, its raw material includes following weight percents:
。
Polyimide foams the most according to claim 1, it is characterised in that: also include the fire retardant that percentage by weight is 4～20%.
Polyimide foams the most according to claim 1, it is characterised in that: described dianhydride is aromatic dianhydride.
Polyimide foams the most according to claim 3, it is characterised in that: the percentage by weight of described aromatic dianhydride is 30～60%, and the percentage by weight of isocyanates is 10～50%.
Polyimide foams the most according to claim 3, it is characterised in that: described aromatic dianhydride be pyromellitic acid anhydride, 3,3 ' 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ' 4,4 '-diphenyl thio-ether tetrformate dianhydride, 4,4 '-diphenyl ether dianhydride, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3 ' 4,4 '-biphenyl dianhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and 3,3', one or more in 4,4'-triphen bis ether tetracarboxylic acid dianhydrides；
Described foaming agent is one or more in water, methanol, ethanol, acetone, ethylene glycol monobutyl ether, butyl glycol ether, ethylene glycol-600, Chlorofluorocarbons (CFCs), hydrogen fluorohydrocarbon, triethylamine and oxolane；
Described polar solvent is one or more in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone；
Described catalyst is one or more in amines catalyst and/or metallic catalyst；
Described surfactant is siloxane type surfactants；
Described isocyanates is one or more in aromatic isocyanate and/or aliphatic isocyanates and/or aryl nitrone isocyanates.
Polyimide foams the most according to claim 5, it is characterised in that: described siloxane type surfactants is one or more in polyether modified silicon oil, polyether modified siloxane, water-soluble silicon oil, silicone, silicone glycol copolymer and organic silicon polyether copolymer surfactants；
Described isocyanates is one or more in methyl diphenylene diisocyanate, methyl diisocyanate, polyphenyl polymethylene polyisocyanates, poly aromatic isocyanate, modified diphenylmethane diisocyanate, hexamethylene diisocyanate, isofoer diisocyanate and XDI.
7. the preparation method of a Polyimide foams, it is characterised in that: comprise the following steps:
(1) dianhydride taking 10～70 weight portions is dissolved in the polar solvent of 10～40 weight portions；
(2) in the solution that step (1) prepares, add partial foaming agent, obtain the first solution；
(3) take the surfactant of 2～20 weight portions, 0.1～8 weight portion catalyst, 4～20 weight portion fire retardant and residue foaming agent mix homogeneously, obtain the second solution；
(4) by the first solution and the second solution mix homogeneously；
(5) take in the mixed liquor of isocyanates addition step (4) gained of 5～70 weight portions, carry out mixed at high speed process；
(6) rapid being poured into by the mixed liquor of step (5) gained in the container for foaming carries out foaming process, then carries out microwave radiation processing or heat treatment, i.e. prepares described Polyimide foams.
The preparation method of Polyimide foams the most according to claim 7, it is characterised in that: the rotating speed carrying out mixed at high speed process described in step (5) is 800～4500rpm.
The preparation method of Polyimide foams the most according to claim 7, it is characterised in that: the power carrying out microwave radiation processing described in step (6) is 0.1～0.5kw/kg foam, and the temperature carrying out heat treatment is 150～250 DEG C.
The preparation method of Polyimide foams the most according to claim 7, it is characterized in that: described step (1) is specially in the polar solvent that the dianhydride of formula ratio joins the formula ratio that temperature is 90～130 DEG C, constant temperature stirring makes dianhydride dissolve, and then solution is cooled to 70～85 DEG C；
Described step (2) is specially and partial foaming agent is added in the solution that step (1) prepares, and after stirring and dissolving, solution is cooled to 30～50 DEG C；
It is 5～20S that described step (5) is specially the incorporation time of the first solution and the second solution.Described step (6) is specially to be poured into by the mixed liquor of step (5) gained rapidly in the container for foaming and foams, when foam surface is the most tacky, when epidermis is hardening, it is carried out microwave radiation processing or carries out heat treatment, foams gradually become glassy yellow, show foams imidization completely, prepare described Polyimide foams.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103241.3A CN106032433A (en) | 2015-03-09 | 2015-03-09 | Polyimide foamed material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103241.3A CN106032433A (en) | 2015-03-09 | 2015-03-09 | Polyimide foamed material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106032433A true CN106032433A (en) | 2016-10-19 |
Family
ID=57149607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510103241.3A Pending CN106032433A (en) | 2015-03-09 | 2015-03-09 | Polyimide foamed material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106032433A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108948409A (en) * | 2018-06-12 | 2018-12-07 | 常州天晟新材料股份有限公司 | A kind of sound absorption Polyimide foams and preparation method thereof |
| CN109810251A (en) * | 2019-01-15 | 2019-05-28 | 哈尔滨工程大学 | A kind of preparation method of high-performance rigid polyimides heat insulation and acoustic absorption foam |
| CN110655790A (en) * | 2019-09-27 | 2020-01-07 | 贵州航天天马机电科技有限公司 | Production method of polyimide foam material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599365A (en) * | 1983-12-27 | 1986-07-08 | John Gagliani | Foaming and curing polyimide resins by application of microwave energy |
| US6172127B1 (en) * | 1997-09-12 | 2001-01-09 | Korea Research Institute Of Chemical Technology | Preparation of polyimide foam |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN102093714A (en) * | 2010-12-22 | 2011-06-15 | 北京航空航天大学 | Light flexible polymide foam material and preparation method thereof |
-
2015
- 2015-03-09 CN CN201510103241.3A patent/CN106032433A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599365A (en) * | 1983-12-27 | 1986-07-08 | John Gagliani | Foaming and curing polyimide resins by application of microwave energy |
| US6172127B1 (en) * | 1997-09-12 | 2001-01-09 | Korea Research Institute Of Chemical Technology | Preparation of polyimide foam |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN102093714A (en) * | 2010-12-22 | 2011-06-15 | 北京航空航天大学 | Light flexible polymide foam material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108948409A (en) * | 2018-06-12 | 2018-12-07 | 常州天晟新材料股份有限公司 | A kind of sound absorption 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 |
| CN109810251A (en) * | 2019-01-15 | 2019-05-28 | 哈尔滨工程大学 | A kind of preparation method of high-performance rigid polyimides heat insulation and acoustic absorption foam |
| CN109810251B (en) * | 2019-01-15 | 2021-10-26 | 哈尔滨工程大学 | Preparation method of high-performance rigid polyimide heat-insulation sound-absorption foam |
| CN110655790A (en) * | 2019-09-27 | 2020-01-07 | 贵州航天天马机电科技有限公司 | Production method of polyimide foam material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101812232B (en) | Polyimide foam and preparation method thereof | |
| CN105924649B (en) | A kind of Polyimide foams and preparation method thereof | |
| US7541388B2 (en) | Polyimide foams | |
| CN106032433A (en) | Polyimide foamed material and preparation method thereof | |
| CN107540839B (en) | Light sound-absorbing heat-insulating polyimide foam material and preparation method thereof | |
| CN110028668B (en) | Preparation method of hard polyimide foam material | |
| CN102093714B (en) | Light flexible polymide foam material and preparation method thereof | |
| WO2015180063A1 (en) | Method for continuously preparing solvent-free open-cell and closed-cell polyimide foam | |
| CN108715636B (en) | Halogen-free flame-retardant polyimide foam material and preparation method thereof | |
| CN107540841B (en) | Preparation method of hard closed-cell polyimide foam | |
| CN103897395A (en) | Preparation method of hydrotalcite and polyimide composite foam material | |
| CN101735457B (en) | Production method of soft polyimide foam | |
| CN108948409A (en) | A kind of sound absorption Polyimide foams and preparation method thereof | |
| CN102134396A (en) | Light flexible polyimide foam material and preparation method thereof | |
| CN105017769A (en) | Cellular reinforcement thermosetting hard closed-cell polyimide foam composite material as well as preparation method and application thereof | |
| CN111592649A (en) | Low-thermal-conductivity polyimide foam material and preparation method thereof | |
| CN104559201A (en) | Method for preparing polyimide-organic silicon composite foam material | |
| CN111793237A (en) | Production method of rigid polyimide foam material | |
| CN103030763A (en) | Polyimide modified polyisocyanurate foam and preparation method thereof | |
| CN113788979B (en) | Hard closed-cell polyimide foam and preparation method thereof | |
| US4738990A (en) | Fire resistant foam composed of predominantly amide and imide linkages | |
| CN109553743A (en) | A kind of Inorganic Fillers Filled high temperature resistant foamed material and preparation method thereof | |
| KR19990025577A (en) | Method for producing polyimide foam | |
| CN115010925A (en) | Polyimide foam material with interlocking double-network structure, and preparation method and application thereof | |
| CN102850569A (en) | Preparation method of polyimide foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161019 |