CN101011874A - Lightening fire resistant polymer porous membrane laminated composite material and manufacturing method thereof - Google Patents
Lightening fire resistant polymer porous membrane laminated composite material and manufacturing method thereof Download PDFInfo
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- CN101011874A CN101011874A CN 200710066794 CN200710066794A CN101011874A CN 101011874 A CN101011874 A CN 101011874A CN 200710066794 CN200710066794 CN 200710066794 CN 200710066794 A CN200710066794 A CN 200710066794A CN 101011874 A CN101011874 A CN 101011874A
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- 238000004519 manufacturing process Methods 0.000 title 1
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- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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Landscapes
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a light heat resistant polymer porous film layer laminated composite material and its making. It is mainly made of porous polymer thin film and reinforced glass fiber, carbon fiber knitting and metal wire net. It firstly makes the porous polymer thin film through phase inversion or thermal phase separation, combining the glass fiber, carbon knitting fiber and metal wire net thorough dipping or heat pressure to make the single or multi layer laminated composite material. It is easy in process, equipment and realization. The made material is light, heat resistant, high in strength, low heat conductivity, good insulation, flexible, and good in machining.
Description
Technical field
The present invention relates to a kind of lightening fire resistant polymer porous membrane laminated composite material and preparation method thereof, be specifically related to a kind of Aeronautics and Astronautics with high temperature resistant, ultralight matter and have the preparation method of the polymer porous membrane laminated composite material of heat-proof quality.
Background technology
Polymer porous film material is the composite of a class by polymer and air two phase compositions, and wherein air is a decentralized photo, and polymer is for connecting phase.Porous material is replaced by gas owing to the partial volume polymer, thereby it is little to have density, the characteristics of light weight.Because the thermal conductivity of gas is than the low nearly order of magnitude of thermal conductivity of polymer, thereby for non-porous polymer, porous material has lower thermal conductivity and two big heat-proof qualities are arranged.Porous material can not reflect or transmit it by absorbing the energy of sound wave, plays the effect of eliminating resonance, minimizing noise, has good characteristics such as heat insulation, sound absorption and buffering.Many polymer can be made porous film material, and comparatively commonly used have polypropylene, polyethylene, Kynoar, polyvinyl chloride, polyurethane, a phenolic aldehyde etc.Compare with common polymer porous material, fire resistant polymer porous membrane material (polyimides, polytetrafluoroethylene (PTFE), polyether-ether-ketone, polyethersulfone ketone, polyphenylene sulfide) except the general character with porous material, also have the following advantages: (1) can anti-high, utmost point low temperature, can be-250-250 ℃ medium-term and long-term the use; (2) excellent flame-retardant performance and self-extinguishment, release cigarette and toxic gas are few under flame condition, and capability of resistance to radiation is strong; (3) have high strength, high-modulus, high-fracture toughness, dimensional stability is better, and linear expansion coefficient is less, can substitution of Al make various airplane components with other metal material; (4) have outstanding tribological property, anti-skimming wear and fretting wear excellent performance especially can descend high wearability of maintenance and low coefficient of friction at 250 ℃, and fatigue resistance is good; (5) the heat-resisting water of chemically-resistant solvent.This kind material has widely in high-tech sectors such as Aeronautics and Astronautics, military affairs, mechanical chemical industry, electronic apparatus, microelectronics and uses owing to have above good performance, and exploitation prospect is very wide.
The heat-resistant polymer material is owing to have excellent performance, and people are strong with this material and height ratio usually, height ratio mould and resistant to elevated temperatures carbon fibre material carry out compound to prepare high abrasion and high mechanical properties special material.Patent No.02141726.1 has reported the polyether-ether-ketone laminar composite that a kind of carbon fibre fabric strengthens, the present invention mainly is by adding various lubricants such as graphite powder, polytetrafluoroethylene (PTFE), carbon fiber etc. as matrix in polyether-ether-ketone, and adopting carbon fiber or graphite fiber fabric is wild phase.This material not only has high mechanical properties, and has high-wearing feature, is mainly used in friction means.But this material does not have microcellular structure, thereby the heat-proof quality of this material is relatively poor.Along with the development of space flight, aviation and some special dimensions, higher and more complicated in recent years to the performance requirement of material.Patent No.03143419.3 has reported a kind of preparation method of porous material of fire resistant polyimide, this material is mainly foamed material, by using the foaming mould of different structure, the polyimide foam shape that obtains is respectively sheet, tubulose in the preparation process.And adopt different blowing ratios can control the density and the preparation tiny balloon of foam.The foamed material that this invention obtains has high temperature resistant/low temperature, anti-combustion, heat insulation/sound insulation property.It is poor that but the shortcoming of this foamed material is a pliability, can not twine or coiling and mechanical strength relatively poor.Patent (application number 200610053038.8 and 20061053271.9) has proposed a kind of technology of preparing with honeycomb structure structure polyimide film dielectric material, the polyimide film internal holes that obtains is that size is in the 5-2000 nanometer, the dielectric constant of film can be reduced to 2.4, is a kind of good ultra-low dielectric constant material.In order to obtain a kind of certain pliability that both had, the porous material that has high mechanical strength again, we have proposed to have the stacked composite study technology of alveolate texture polymer film, this material promptly has the lightweight of polyimide foam material, heat insulation, heat resistance, has certain pliability and high machinery again slightly.This lightening fire resistant composite all has great application prospect in space flight, aviation field and some military and civilian fields etc.
Summary of the invention
The purpose of this invention is to provide a kind of fire resistant polymer porous membrane laminated composite material and preparation method thereof.
Lightening fire resistant polymer porous membrane laminated composite material, handled by dip-coating, continuous hot-press or be hot pressed into one by resistant to elevated temperatures polymer porous film and carbon fiber preform, fiberglass braided thing or woven wire, the structure of polymer porous film is an alveolate texture.
The material of described resistant to elevated temperatures polymer porous film is polyimides, polyether-ether-ketone, polyethersulfone ketone, polyethersulfone ketone or polyphenylene sulfide.
Described polyimide porous membrane is to be prepared from by the solution inversion of phases by the precursor polyamic acid of polyimides or polyesteramide, and polyimide porous membrane has the repeat unit structure that following general formula is represented:
Wherein, Ar
1Structure is:
Ar
2Structure is:
Dianhydride monomer in the described polyimide film be pyromellitic acid dianhydride (PMDA) or 3,3 ', 4,4 '-in the benzophenone tetracarboxylic dianhydride (BTDA) any one; Diamine monomer in the described polyimide film is 4,4 '-in diaminodiphenyl ether (ODA) or the p-phenylenediamine (PDA) any one.
Described woven wire is copper mesh, stainless steel or aluminium alloy net, and the thickness of woven wire is 0.1-0.5mm, the aperture 0.2-0.5mm of woven wire.
The preparation method's of lightening fire resistant polymer porous membrane laminated composite material step is:
1) carbon fiber preform, fiberglass braided thing or woven wire are cut into the sheet material of 20 * 10cm, and in ultrasonic wave, clean, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone;
2) precursor polyamic acid or the polyesteramide with heat-resistant polymer, polyimides is dissolved in the polar solvent respectively, being configured to mass concentration respectively is 15～40% heat-resistant polymer, the precursor polyamic acid or the polyesteramide film making solution of polyimides, prepare the precursor polyamic acid perforated membrane or the polyesteramide perforated membrane of fire resistant polymer porous membrane, polyimides then by phase inversion or thermally induced phase separation, and extract and dry the processing;
3) cleaned carbon fiber preform, fiberglass braided thing or woven wire be impregnated in respectively in the film making solution of above-mentioned correspondence, under ultrasonic wave, fully flood 10～30min, and to carry out single or multiple lift by dip-coating, continuous hot-press or hot pressing mode compound with corresponding above-mentioned perforated membrane respectively, and densified, planarizing process is carried out on the surface of laminated composite material;
4) the single or multiple lift porous membrane laminated composite material after densified is carried out post processing, and dry.
Described laminated composite material is densified, planarizing process technology is: the surface of the laminated composite material of the precursor polyamic acid of heat-resistant polymer, polyimides or polyesteramide perforated membrane is applied the film making solution corresponding with it respectively, and dry.
Described dip-coating, hot-pressing processing step are: with precursor polyamic acid perforated membrane or polyesteramide perforated membrane and carbon fiber preform, glass fibers braid or the corresponding film making solution of woven wire surface difference dip-coating of polyimides, carry out the compound and continuous hot-press processing of single or multiple lift then, condition is: under hot pressing pressure 3MPa, and heat treatment 2 hours under 1 hour, 320 ℃ temperature of heat treatment under 1 hour, 220 ℃ temperature of heat treatment under 100 ℃ of temperature.
The compound step of described hot pressing is: be put in fire resistant polymer porous membrane and carbon fiber preform, glass fibers braid or woven wire on the hot press in order, at 300～330 ℃, hot pressing pressure is 3～6Mpa, hot pressing time is 10～20min, after the hot pressing, quenching in 0～80 ℃ water;
Advantage of the present invention is:
The fire resistant polymer porous membrane laminated composite material that the present invention is prepared, owing to adopted polymer porous film material, thereby it is little to have density, light weight, the characteristics that thermal conductivity is low and heat-proof quality is good, but also can control the density of the pore size of material as required with the reduction porous material.With the compound material of making heat insulation, heatproof and ultralight, high-mechanical property of porous film material and woven wire or carbon fiber or fiberglass braided thing, efficiently solve at present used material load among the present invention than shortcoming great, the thermal insulation difference.The fire resistant polymer porous membrane laminated composite material that the present invention is prepared, it is compound to carry out single or multiple lift as required, but also can twine as required or reel, and is prepared into different shapes and assembly to satisfy different needs.This material is expected to be used for high temperature resistant, the heat insulation parts of the higher space flight of serviceability temperature, aviation aircraft or to be used for some military or civilian fields, has good application prospects.
The specific embodiment
The present invention makes this porous film material and reinforcing material (woven wire, glass or carbon fiber preform) strengthen design by the fire resistant polymer porous membrane material of preparation certain pore size and porosity then, improves the mechanical strength of polymer porous film greatly.Can overcome that homogenous material intensity is low, be easy to generate fine fisssure in the poor toughness, high temperature use through reinforced composite materials, have a strong impact on its serviceability.The polymer porous membrane laminated composite material that the present invention is prepared, not only have good heat endurance and mechanical strength, and lightweight, durable, combine the advantage of metal material, carbon fiber and special engineering plastics and porous film material, on performance, played collaborative effect, obtain the incomparable superior combination property of homogenous material, become the new composite of a class, can be widely used in defence and military departments such as aerospace, guided missile, rocket, atomic energy, and then extend to some civilian departments.
The present invention forms stacked reinforced composite by the fire resistant polymer porous membrane material of certain pore size and porosity and woven wire, carbon fiber or fiberglass braided thing are strengthened design, so that this composite has high temperature resistant/low temperature, heat insulation, proportion ultralight, good toughness, mechanical performance advantages of higher.By to heat-resistant polymer film fenestra size, porosity and thickness measurement, and the mensuration of laminated composite material interlaminar shear strength, characterize the performance of laminated composite material.
Among the present invention, the assay method of polymer porous film membrane structure and shear strength is respectively:
Film thickness determination: mainly measure the thickness of dry film in the composite, adopt micrometer caliper to measure, choose 5 measuring points and average.
The porosity of film and the mensuration of average pore size: adopt mercury injection apparatus (DEMO AutoPore9500, the U.S.) to measure.The laminated composite material interlaminar shear strength is pressed the GB3357282 standard, carries out on Zwick/Roell Z020 universal testing machine.The compression strength of laminated composite material is carried out on Zwick/Roell Z020 universal testing machine, and loading velocity is 0.1mm/s.
Below in conjunction with hereinafter embodiment the present invention is done more detailed description, but described embodiment is not construed as limiting the invention.
Embodiment 1
With the carbon fiber preform is reinforcing material, carries out compound preparation porous membrane laminated composite material with polyimide porous membrane, and concrete steps are as follows:
1. carbon fiber preform is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. make the precursor polyamic acid of polyimides be dissolved in polar organic solvent N, obtain mass concentration in the N-dimethylacetylamide (DMAc) and be 15% preparation liquid; With preparation liquid after filtration, to spread to thickness on the stainless steel supporter be 100 microns liquid film for degassing back; Liquid film stopped to immerse in 20 ℃ of coagulating baths behind the certain hour in air solidified 10 minutes; Film after the curing cleans with alcohol immersion, obtains having the polyamic acid precursor film of loose structure after the drying.
3. cleaned carbon fiber preform be impregnated in the N of 15% polyimide precursor thing, in the N-dimethylacetamide solution, under ultrasonic wave, fully flood 30min.
4. after the polyamic acid precursor film surface of preparation in the above-mentioned steps 2 being cleaned with DMAc, be immersed in the N of 15% polyester-polyamide acid precursors then, 5min in the N-dimethylacetamide solution, the carbon fiber control of two-dimensional braided thing that takes out in back and the step 3 bonds together, and is prepared into the single or multiple lift composite.
5. adopt the mode of continuous hot-press processing, laminated composite material prepared in the step 4 heat-treated in nitrogen be converted into polyimide film laminated composite material with loose structure, the temperature and time of hot-pressing processing is: under hot pressing pressure 3MPa, 100 ℃ following 1 hour, 220 ℃ following 1 hours, 320 ℃ are following 2 hours.
6. the composite after the hot-pressing processing is extracted processing, and dry.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 1.
Embodiment 2
With fiberglass braided thing is reinforcing material, carries out compound preparation porous membrane laminated composite material with polyimide porous membrane, and concrete steps are as follows:
1. fiberglass braided thing is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. make the precursor polyamic acid of polyimides be dissolved in polar organic solvent N, obtain mass concentration in the N-dimethylacetylamide (DMAc) and be 20% preparation liquid; With preparation liquid after filtration, to spread to thickness on the stainless steel supporter be 200 microns liquid film for degassing back; Liquid film stopped to immerse in 20 ℃ of coagulating baths behind the certain hour in air solidified 30 minutes; Film after the curing cleans with alcohol immersion, obtains having the polyamic acid precursor film of loose structure after the drying.
3. cleaned glass fibre three-dimensional braid be impregnated in the N of 20% polyimide precursor thing, in the N-dimethylacetamide solution, under ultrasonic wave, fully flood 30min.
4. after the polyamic acid precursor film surface of preparation in the above-mentioned steps 2 being cleaned with DMAc, be immersed in the N of 20% polyimide precursor thing then, 5min in the N-dimethylacetamide solution, the braid that takes out the glass fibre in back and the step 3 bonds together, and is prepared into the single or multiple lift composite.
5. the mode that adopts continuous hot-press to handle is heat-treated laminated composite material prepared in the step 4, and the temperature and time of hot-pressing processing is: under hot pressing pressure 3MPa, 100 ℃ following 1 hour, 220 ℃ following 1 hours, 320 ℃ are following 2 hours.
6. the composite after the hot-pressing processing is extracted processing, and dry.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 1.
Embodiment 3
With the copper mesh is reinforcing material, carries out compound preparation porous membrane laminated composite material with polyimide porous membrane, and concrete steps are as follows:
1. copper mesh is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. make the precursor polyesteramide of polyimides be dissolved in polar organic solvent N, obtain mass concentration in the N-dimethylacetylamide (DMAc) and be 30% preparation liquid; With preparation liquid after filtration, to spread to thickness on the stainless steel supporter be 400 microns liquid film for degassing back; Liquid film stopped to immerse in 20 ℃ of coagulating baths behind the certain hour in air solidified 30 minutes; Film after the curing obtains having the polyamide ester precursor film of loose structure with ethanol or acetone soaking and washing after the drying.
3. cleaned copper mesh impregnated in the N of 30% polyimide precursor thing, in the N-dimethylacetamide solution, fully floods 30min under ultrasonic wave.
4. after the polyamide ester precursor film surface of preparation in the above-mentioned steps 2 being cleaned with DMAc, be immersed in the N of 30% polyimide precursor thing then, 5min in the N-dimethylacetamide solution, the copper mesh that takes out in back and the step 3 bonds together, and is prepared into the single or multiple lift composite.
5. the mode that adopts continuous hot-press to handle is heat-treated laminated composite material prepared in the step 4, and the temperature and time of hot-pressing processing is: under hot pressing pressure 3MPa, 100 ℃ following 1 hour, 220 ℃ following 1 hours, 320 ℃ are following 2 hours.
6. the composite after the hot-pressing processing is extracted processing, and dry.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 1.
Embodiment 4
With fiberglass braided thing is reinforcing material, carries out compound preparation porous membrane laminated composite material with the polyethersulfone ketone perforated membrane, and concrete steps are as follows:
1. fiberglass braided thing is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. polyethersulfone ketone being dissolved in obtain in the polar organic solvent N-N-methyl-2-2-pyrrolidone N-(NMP) mass concentration is 20% preparation liquid; With preparation liquid after filtration, to spread to thickness on glass support be 200 microns liquid film for degassing back; To solidify 30 minutes in 20 ℃ of coagulating baths of liquid film immersion; Film after the curing cleans with alcohol immersion, obtains having the polyethersulfone ketone perforated membrane of loose structure after the drying.
3. cleaned glass fibre control of two-dimensional braided thing impregnated in the nmp solution of 20% polyethersulfone ketone, fully floods 30min under ultrasonic wave.
4. after the polyethersulfone ketone surface of preparation in the above-mentioned steps 2 being cleaned with NMP, be immersed in 2min in the nmp solution of 20% polyethersulfone ketone then, take out the back and bond together, be prepared into bilayer or multilayer materials with fiberglass braided thing in the step 3.
5. laminated composite material prepared in the step 4 is carried out drying in nitrogen, desolvate to remove.
So the stacked performance of composites of polyalcohol stephanoporate that obtains is shown in Table 1.
The performance of table 1 polyimides, polyethersulfone ketone porous membrane laminated composite material
| Thickness (μ m) | Film average pore size μ m | Porosity (%) | Compression strength (MPa) | Shear strength (MPa) | |
| Embodiment 1 | 30 | 1.10 | 85％ | 4.2 | 13.55 |
| Embodiment 2 | 65 | 0.85 | 72％ | 7.5 | 27.33 |
| Embodiment 3 | 170 | 0.55 | 45％ | 9.3 | 39.65 |
| Embodiment 4 | 150 | 1.25 | 80％ | 3.6 | 9.34 |
Embodiment 5
With the carbon fiber preform is reinforcing material, with polyether-ether-ketone porous film carry out compound with the preparation porous membrane laminated composite material, concrete steps are as follows:
1. carbon fiber preform is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. be that diluent stir make its melt blending, matrix concentration be 20% at 310 ℃ at benzophenone with polyether-ether-ketone.Mix the back and take out, be placed on rapidly under the room temperature and cool off, treat promptly to obtain polyether-ether-ketone/benzophenone blend after the sample solidifies.Then this blend is hot pressed into 20cm * 10cm at 280 ℃, the initial diaphragm of 200 micron thickness.
3. the diaphragm with step 2 preparation is placed on (can be one or more layers) on the carbon fiber preform, then on hot press at 300 ℃, hot pressing 10min under the 3MPa, the sample after the hot pressing is quenching in 0 ℃ of water.Sample after the hot pressing extracts in acetone 2 times, so that diluent is removed fully.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 2.
Embodiment 6
With the carbon fiber preform is reinforcing material, with polyether-ether-ketone porous film carry out compound with the preparation porous membrane laminated composite material, concrete steps are as follows:
1. the braid of carbon fiber is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. be that diluent stirs that to make its melt blending, matrix concentration be 30% with polyether-ether-ketone with the benzophenone at 320 ℃.Mix the back and take out, be placed on rapidly under the room temperature and cool off, treat promptly to get polyether-ether-ketone/benzophenone blend after the sample solidifies.Then this blend is hot pressed into 20cm * 10cm at 280 ℃, the initial diaphragm of 300 micron thickness.
3. the diaphragm of step 2 preparation is placed on the braid of carbon fiber (can be one or more layers), on hot press, at 320 ℃, hot pressing 10min under the 4MPa, the sample after the hot pressing are placed on quenching in 30 ℃ of water then.Sample after the hot pressing extracts in acetone 2 times, so that diluent is removed fully.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 2.
Embodiment 7
With the stainless (steel) wire is reinforcing material, carries out compound preparation porous membrane laminated composite material with the polyethersulfone ketone perforated membrane, and concrete steps are as follows:
1. stainless (steel) wire is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. be that diluent stirs that to make its melt blending, matrix concentration be 30% with polyether-ether-ketone with the benzophenone at 330 ℃.Mix the back and take out, be placed on rapidly under the room temperature and cool off, treat promptly to obtain polyether-ether-ketone/benzophenone blend after the sample solidifies.Then this blend is hot pressed into 20cm * 10cm at 280 ℃, the initial diaphragm of 400 micron thickness.
3. the diaphragm with step preparation 2 evenly is layered on (can be one or more layers) on the stainless (steel) wire, then on hot press at 330 ℃, hot pressing 10min under the 5MPa, the sample after the hot pressing is quenching in 50 ℃ of water.Product after the hot pressing extracts in acetone 3 times, so that diluent is removed fully.
So the stacked performance of composites of polyalcohol stephanoporate that obtains is shown in Table 2.
Embodiment 8
With the aluminium alloy net is reinforcing material, is that polymeric material prepares porous membrane laminated composite material with the polyether-ether-ketone, and concrete steps are as follows:
1. the aluminium alloy net is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. be that diluent stirs that to make its melt blending, matrix concentration be 40% with polyether-ether-ketone with the benzophenone at 330 ℃.Mix the back and take out, after mixing, be placed on rapidly under the room temperature and cool off, treat promptly to obtain polyether-ether-ketone/benzophenone blend after the sample solidifies.Then this blend is hot pressed into 20cm * 10cm at 280 ℃, the initial diaphragm of 500 micron thickness.
3. the diaphragm with step 2 preparation evenly is layered on aluminium alloy online (can be one or more layers), then on hot press at 330 ℃, hot pressing 10min under the 6MPa, the sample after the hot pressing is quenching in 80 ℃ of water.Product after the hot pressing extracts in acetone 3 times, so that diluent is removed fully.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 2.
Embodiment 9
Braid with carbon fiber is a reinforcing material, is that polymeric material prepares porous membrane laminated composite material with the polyphenylene sulfide, and concrete steps are as follows:
1. the braid of carbon fiber is cut into the sheet material of 20 * 10cm, and in ultrasonic wave, cleans, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone.
2. be diluent stirring make its melt blending, matrix concentration be 30% after to take out at 330 ℃ with the benzophenone with polyphenylene sulfide, after mixing, be placed on rapidly under the room temperature and cool off, treat promptly to obtain polyether-ether-ketone/benzophenone blend after the sample solidifies.Then this blend is hot pressed into 20cm * 10cm at 280 ℃, the initial diaphragm of 500 micron thickness.
3. the diaphragm of step preparation 2 evenly is layered on the braid of woven wire or carbon fiber (can be one or more layers), then on hot press at 310 ℃, hot pressing 10min under 6MPa, the sample after the hot pressing is quenching in 30 ℃ of water.Product after the hot pressing extracts in acetone 3 times, so that diluent is removed fully.
So the performance of the polymer porous membrane laminated composite material that obtains is shown in Table 2.
The performance of table 2 polyether-ether-ketone, polyphenylene sulfide porous film laminated composite material
| Thickness (μ m) | Film average pore size μ m | Porosity (%) | Compression strength (MPa) | Shear strength (MPa) | |
| Embodiment 5 | 70 | 0.43 | 59％ | 6.4 | 12.88 |
| Embodiment 6 | 90 | 1.25 | 87％ | 4.7 | 16.95 |
| Embodiment 7 | 120 | 1.11 | 78％ | 5.3 | 20.11 |
| Embodiment 8 | 150 | 0.53 | 56％ | 9.5 | 23.44 |
| Embodiment 9 | 190 | 0.49 | 48％ | 7.6 | 18.76 |
Claims (9)
1. lightening fire resistant polymer porous membrane laminated composite material, it is characterized in that, by dip-coating, continuous hot-press or be hot pressed into one, the structure of polymer porous film is an alveolate texture by resistant to elevated temperatures polymer porous film and carbon fiber preform, fiberglass braided thing or woven wire for it.
2. a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 1 is characterized in that, the material of described resistant to elevated temperatures polymer porous film is polyimides, polyether-ether-ketone, polyethersulfone ketone or polyphenylene sulfide.
3. a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 2, it is characterized in that, described polyimide porous membrane is to be prepared from by the solution inversion of phases by the precursor polyamic acid of polyimides or polyesteramide, and polyimide porous membrane has the repeat unit structure that following general formula is represented:
Wherein, Ar
1Structure is:
Ar
2Structure is:
4. a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 3, it is characterized in that, the dianhydride monomer in the described polyimide film be pyromellitic acid dianhydride (PMDA) or 3,3 ', 4,4 '-in the benzophenone tetracarboxylic dianhydride (BTDA) any one; Diamine monomer in the described polyimide film is 4,4 '-in diaminodiphenyl ether (ODA) or the p-phenylenediamine (PDA) any one.
5. a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 1, it is characterized in that, described woven wire is copper mesh, stainless steel or aluminium alloy net, and the thickness of woven wire is 0.1-0.5mm, the aperture 0.2-0.5mm of woven wire.
6. the preparation method of a lightening fire resistant polymer porous membrane laminated composite material is characterized in that, the step of method is:
1) carbon fiber preform, fiberglass braided thing or woven wire are cut into the sheet material of 20 * 10cm, and in ultrasonic wave, clean, put then to dry by the fire in the baking oven to acetone and volatilize fully with acetone;
2) precursor polyamic acid or the polyesteramide with heat-resistant polymer, polyimides is dissolved in the polar solvent respectively, being configured to mass concentration respectively is 15～40% heat-resistant polymer, the precursor polyamic acid or the polyesteramide film making solution of polyimides, prepare the precursor polyamic acid perforated membrane or the polyesteramide perforated membrane of fire resistant polymer porous membrane, polyimides then by phase inversion or thermally induced phase separation, and extract and dry the processing;
3) cleaned carbon fiber preform, fiberglass braided thing or woven wire be impregnated in respectively in the film making solution of above-mentioned correspondence, under ultrasonic wave, fully flood 10～30min, and handle by dip-coating, continuous hot-press with corresponding above-mentioned perforated membrane respectively or hot pressing mode to carry out single or multiple lift compound, and densified, planarizing process is carried out on the surface of laminated composite material;
4) the single or multiple lift porous membrane laminated composite material after densified is carried out the back extraction and handle, and dry.
7. the preparation method of a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 6, it is characterized in that, described laminated composite material is densified, planarizing process technology is: the surface of the laminated composite material of the precursor polyamic acid of heat-resistant polymer, polyimides or polyesteramide perforated membrane is applied the film making solution corresponding with it respectively, and dry.
8. the preparation method of a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 6, it is characterized in that, described dip-coating, the continuous hot-press treatment step is: with precursor polyamic acid perforated membrane or the polyesteramide perforated membrane and the carbon fiber preform of polyimides, glass fibers braid or woven wire surface be the corresponding film making solution of dip-coating respectively, carry out the compound and continuous hot-press processing of single or multiple lift then, condition is: under hot pressing pressure 3MPa, heat treatment is 1 hour under 100 ℃ of temperature, heat treatment is 1 hour under 220 ℃ of temperature, heat treatment is 2 hours under 320 ℃ of temperature.
9. the preparation method of a kind of lightening fire resistant polymer porous membrane laminated composite material according to claim 6, it is characterized in that, the compound step of described employing hot pressing is: be put in fire resistant polymer porous membrane and carbon fiber preform, glass fibers braid or woven wire on the hot press in order, at 300～330 ℃, hot pressing pressure is 3～6Mpa, hot pressing time is 10～20min, after the hot pressing, and quenching in 0～80 ℃ water.
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