CN1807510A - Thermoplastic polyimide microporous material and preparation process thereof - Google Patents
Thermoplastic polyimide microporous material and preparation process thereof Download PDFInfo
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- CN1807510A CN1807510A CN200610038175.7A CN200610038175A CN1807510A CN 1807510 A CN1807510 A CN 1807510A CN 200610038175 A CN200610038175 A CN 200610038175A CN 1807510 A CN1807510 A CN 1807510A
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- microporous material
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- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 41
- 239000012229 microporous material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 abstract description 29
- 229920001721 polyimide Polymers 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 26
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 10
- 239000004033 plastic Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000004223 radioprotective effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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Abstract
The invention relates to the technical field of preparation of microporous polymer materials, in particular to a thermoplastic polyimide microporous material and a preparation process thereof. The preparation raw materials comprise the following components in percentage by weight: thermoplastic Polyimide (TPI): 70% -95%; pore-forming agent: 5 to 30 percent. The microporous material is prepared by adopting a powder sintering method of wet mixing of polyimide and a solid pore-forming agent, so that the process flow is simple and the cost is low; the multi-stage constant temperature sintering enables the pore-forming agent to be completely decomposed and polyimide particles to be well bonded, and effectively improves the strength and porosity of the material; the performance of the microporous material can be adjusted by controlling the dosage of the pore-forming agent, and the aperture and the porosity are easy to adjust.
Description
Technical field
The present invention relates to a kind of capillary copolymer material preparing technical field.Relate in particular to a kind of thermoplastic polyimide microporous material and preparation technology thereof.
Background technology
Since nineteen fifty-nine, Massachusetts Polytechnics prepared the nylon poromerics, poromerics was rapidly developed, and its inside has special microvoid structure.Wherein the micropore polyimide material is applied to space flight and aviation, insulation, thermal insulation, fields such as precision optical machinery by performances such as its thermostability, excellent mechanical performances, anti-friction wear-resistants more.Develop the micropore polyimide material since nineteen seventies abroad.In the development of the eighties poromerics rapidly, the U.S. successfully is applied to this material the contour most advanced and sophisticated system of inertial navigation of satellite, aircraft.Compare, domestic starting late, and because foreign technology blocks slower development.
At present, the method and the technology of producing poromerics are many, but the main range of application of various technology of preparing there are differences.The conventional metals powder sintering is to be matrix with the powder, mainly regulate material property by control process parameters, the material of preparation is mainly via material, but because bigger with respect to the viscous deformation of metallic substance polymkeric substance, it is not obvious to the poromerics performance impact to regulate processing parameter.Adopt the supercritical co method to prepare poromerics, its hole size is easy to control, but most for being closed pore, is mainly used in foam and sound-absorbing material.Template prepares the even aperture distribution of material, and material property easily regulates, and removes but template is difficult during aftertreatment, influences material property.
Chinese patent [application publication number CN1593899A] relates to a kind of preparation of polypropylene poromerics.It is matrix with the polypropylene powder, with liquid blowing agent, linking agent and tensio-active agent and polypropylene powder uniform mixing, colds pressing, and sintering prepares material.This method technical process is simple, less investment.Whipping agent can be regulated the porous material performance simultaneously.But because the interpolation of mechanical property of polypropylene own and various auxiliary agents, its over-all properties is poor, the low aspect application requiring such as aerospace, precision instrument that do not meet of heatproof rank.
Chinese patent [application publication number CN1562607A] relates to a kind of preparation of porous polyimide retainer material.This technology is matrix with the polyimide, adopts the constant volume sintering process, promptly according to needed density of material, in the material sintering process material is applied certain pressure.This method can accurately be controlled the porosity of porous material, has improved the reliability of its performance.Yet polymkeric substance and metallic substance are compared, and its viscous deformation is bigger, and the regulation range of colding pressing is limited, thereby have limited the regulation range of pore structure.
United States Patent (USP) [number of patent application US20020058720A1] has proposed a kind of method for preparing the micropore polyimide material.This method adds disperse phase in polyimide matrix, with supercritical co disperse phase is extracted out.The porosity that this method is come control material by the ratio of control disperse phase in mixture.But because the wayward relatively difficulty of the degree of scatter of disperse phase, the processing condition harshness requires high pressure low temperature, the cost height.
United States Patent (USP) [number of patent application US6395677B1] adopts compression molding to prepare the porous polyimide material.Use rice chaff, following 700 ℃～1000 ℃ carbonizations of oxygen free condition, cold pressing in back and polyimide powder uniform mixing, sintering, its product is used for retainer.Product performance are regulated by the control moulding process.But rice chaff carbonization process processing requirement is higher.
Summary of the invention
Technical problem to be solved by this invention: poor in order to overcome the poromerics over-all properties, the shortcoming of complex process proposes a kind of interpolation solid blowing agent wet-mixed, cold-rolled sintered method of adopting and prepares thermoplastic polyimide microporous material.At poromerics complex process problem, the present invention adopts the preparation method of solid pore-forming material and polyimide powder wet-mixed on powder sintered basis.
Technical scheme of the present invention is:
A kind of thermoplastic polyimide microporous material, the composition of its preparation raw material and the weight percentage of each component are respectively:
Thermoplastic polyimide (TPI): 70%～95%
Pore-forming material: 5%～30%
Wherein thermoplastic polyimide is that the fundamental property of thermoplastic polyimide resin is: flexural strength 150～190MPa, and tensile strength 70～110MPa, second-order transition temperature is 〉=250 ℃, shock strength 20～50kJ/m
2, the GCPI that preferred Changzhou extensively becomes novel plastic company limited to produce
TMPowder, it not only has performances such as excellent heat resisting, mechanics, dielectric, corrosion resistant and radioprotective, also shows remarkable hot-work characteristic.
Described pore-forming material is at least a kind of of polyoxyethylene glycol, citric acid, methylcellulose gum or urea element.
The invention allows for a kind of method for preparing above-mentioned thermoplastic polyimide microporous material, it is characterized in that on powder sintered basis, adopting pore-forming material and polyimide powder wet-mixed method to prepare poromerics.With the pore-forming material of weight percentage 5%～30%, 70%～95% thermoplastic polyimide (TPI) wet-mixed, drying is packed the blended composite powder in the mould into, after colding pressing, mould is put into constant temperature heating device sintered heat insulating, the demoulding.
Its technical process is:
The pressure of wherein colding pressing is 20～80MPa; Mould is put into constant temperature heating device, rise to 110～200 ℃ of pore-forming materials, be incubated after 1～2 hour, be warming up to 270～340 ℃, be incubated 1～6 hour from room temperature, cooling naturally, lifting temperature speed is 3～5 ℃ of per minutes.
Wherein thermoplastic polyimide is that the fundamental property of thermoplastic polyimide resin is: flexural strength 150～190MPa, and tensile strength 70～110MPa, second-order transition temperature is 〉=250 ℃, shock strength 20～50kJ/m
2, the GCPI that preferred Changzhou extensively becomes novel plastic company limited to produce
TMPowder, it not only has performances such as excellent heat resisting, mechanics, dielectric, corrosion resistant and radioprotective, also shows remarkable hot-work characteristic, can adopt hot moulding, extrude and the injecting method moulding.
Described pore-forming material is a kind of or many persons mixture of polyoxyethylene glycol, citric acid, methylcellulose gum and urea element.
Polyimide and pore-forming material adopt wet-mixed in the described thermoplastic polyimide microporous material preparation, and it makes pore-forming material uniformly attached to the polyimide particles surface, controls pore size distribution easily.
Sintering process adopts multistage constant temperature sintering in the described thermoplastic polyimide microporous material preparation, by adjusting time and the decomposition of sintering temperature control pore-forming material and two stages of bonding of polyimide, this sintering method makes pore-forming material to decompose fully, and polyimide particles can bond well.
Beneficial effect:
The present invention adopts the powder sintered method of polyimide and solid pore-forming material wet-mixed to prepare poromerics, and technical process is simple, and cost is low; Multistage constant temperature sintering makes pore-forming material decompose fully and the polyimide particles bonds well, has effectively improved the strength of materials and porosity; The performance that control pore-forming material consumption can be regulated poromerics is easy to adjustment aperture and porosity.Mechanical property:
| Performance index | This patent measured value | Literature value |
| Tensile strength/MPa | 35～50 | 17.5～31.5 |
Mean pore size: micropore polyimide material of the present invention is similar to present pore structure both domestic and external, and pore size distribution concentrates on 1 micron.
Oil-retaining power: micropore polyimide material oil length of the present invention is 14%～19%, and the polyimide material oil length of domestic production at present is 10%～15%.
Description of drawings
Fig. 1 is the Electronic Speculum figure of the thermoplastic polyimide microporous material of embodiment 1.
Fig. 2 is the Electronic Speculum figure of the thermoplastic polyimide microporous material of embodiment 4.
Microtexture shows that bonding is good between the polyimide particles, has excellent mechanical property, and is through-hole structure.
Embodiment
Embodiment 1
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 95g thermoplastic polyimide powder
TM-M1 polyimide molding powder) add polyoxyethylene glycol (purity 99.5%, molecular-weight average 20000) 5g in, both adopt wet-mixed, drying, the compound mould of packing into is after colding pressing with the pressure of 20MPa, the demoulding, 160 ℃ of insulations 1 hour, 290 ℃ were incubated 4 hours with compressing tablet.The poromerics porosity that makes is 16.4%, and bending property is 40.9MPa, frictional coefficient 0.06-0.07, volume wear rate: 6.61 * 10
-15m
3/ (Nm).Its structure as shown in Figure 1.
Embodiment 2
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 90g thermoplastic polyimide powder
TM-M1 polyimide molding powder) add citric acid (purity 99.5%) 10g in, both adopt wet-mixed, drying, the compound mould of packing into, after colding pressing with the pressure of 30MPa, the demoulding, with compressing tablet 110 ℃ of insulations 1 hour, 300 ℃ of insulations 2 hours.The poromerics porosity that makes is 21.3%, and bending property is 42.3MPa, frictional coefficient 0.06-0.065, volume wear rate: 4.85 * 10
-15m
3/ (Nm).
Embodiment 3
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 80g thermoplastic polyimide powder
TM-M1 polyimide molding powder) add methylcellulose gum (purity 99.5%) 20g in, both adopt wet-mixed, and drying is packed compound in the mould into, after colding pressing with the pressure of 40MPa, the demoulding, with compressing tablet 180 ℃ of insulations 1 hour, 310 ℃ of insulations 1 hour.The poromerics porosity that makes is 16.4%, and bending property is 35.6MPa, frictional coefficient 0.07-0.08, volume wear rate: 2.81 * 10
-15m
3/ (Nm).
Embodiment 4
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 85g thermoplastic polyimide powder
TM-M1 polyimide molding powder) add urea element (purity 99.5%) 15g in, both are adopted wet-mixed, drying is packed compound in the mould into, after colding pressing with the pressure of 60MPa, the demoulding, with compressing tablet 200 ℃ of insulations 2 hours, 320 ℃ of insulations 2 hours.The poromerics porosity that makes is 25.7%, and bending property is 37.4MPa, frictional coefficient 0.065-0.07, volume wear rate: 3.63 * 10
-15m
3/ (Nm).Its structure as shown in Figure 2.
Embodiment 5
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 75g thermoplastic polyimide powder
TM-M1 polyimide molding powder) adds polyoxyethylene glycol (purity 99.5% in, molecular-weight average 20000) 15g and citric acid (purity 99.5%) 10g, both are adopted wet-mixed, dry, compound is packed in the mould, after colding pressing with the pressure of 70MPa, the demoulding, 160 ℃ of insulations 2 hours, 325 ℃ were incubated 6 hours with compressing tablet.The poromerics porosity that makes is 28%, and bending property is 38.7MPa, frictional coefficient 0.055-0.06, volume wear rate: 2.42 * 10
-15m
3/ (Nm).
Embodiment 6
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 70g thermoplastic polyimide powder
TM-M1 polyimide molding powder) adds citric acid (purity 99.5%) 15g and urea element (purity 99.5%) 15g in, both are adopted wet-mixed, drying, compound is packed in the mould, after colding pressing with the pressure of 75MPa, the demoulding, 200 ℃ of insulations 2 hours, 330 ℃ were incubated 3 hours with compressing tablet.The poromerics porosity that makes is 27%, and bending property is 34.6MPa, frictional coefficient 0.06-0.065, volume wear rate: 2.15 * 10
-15m
3/ (Nm).
Embodiment 7
A kind of thermoplastic polyimide microporous material preparation method comprises following processing step: (Changzhou extensively becomes novel plastic company limited, GCPI at 70g thermoplastic polyimide powder
TM-M1 polyimide molding powder) adds polyoxyethylene glycol 10g and citric acid (purity 99.5%) 10g and methylcellulose gum (purity 99.5%) 10g in, both are adopted wet-mixed, dry, compound is packed in the mould, after colding pressing with the pressure of 80MPa, the demoulding, 180 ℃ of insulations 2 hours, 340 ℃ were incubated 6 hours with compressing tablet.The poromerics porosity that makes is 29%, and bending property is 31.5MPa, frictional coefficient 0.065-0.07, volume wear rate: 2.72 * 10
-15m
3/ (Nm).
Claims (5)
1, a kind of thermoplastic polyimide microporous material is characterized in that preparing the composition of raw material and the weight percentage of each component is respectively:
Thermoplastic polyimide (TPI): 70%～95%
Pore-forming material: 5%～30%.
2, material according to claim 1 is characterized in that the fundamental property of described thermoplastic polyimide is: flexural strength 150～190MPa, and tensile strength 70～110MPa, second-order transition temperature is 〉=250 ℃, shock strength 20～50kJ/m
2
3, material according to claim 1 is characterized in that described pore-forming material is at least a kind of of polyoxyethylene glycol, citric acid, methylcellulose gum or urea element.
4, a kind of preparation technology of above-mentioned materials as claimed in claim 1, its step comprises: with the pore-forming material of weight percentage 5%～30%, 70%～95% thermoplastic polyimide (TPI) wet-mixed, dry, the blended composite powder is packed in the mould, after colding pressing, mould is put into constant temperature heating device sintering, insulation, the demoulding.
5, technology according to claim 4 is characterized in that the pressure of colding pressing is 20～80MPa; Mould is put into constant temperature heating device, rise to 110～200 ℃ of pore-forming materials, be incubated after 1～2 hour, be warming up to 270～340 ℃, be incubated 1～6 hour from room temperature, cooling naturally, lifting temperature speed is 3～5 ℃ of per minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100381757A CN100408636C (en) | 2006-02-07 | 2006-02-07 | Thermoplastic polyimide microporous material and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100381757A CN100408636C (en) | 2006-02-07 | 2006-02-07 | Thermoplastic polyimide microporous material and preparation process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1807510A true CN1807510A (en) | 2006-07-26 |
| CN100408636C CN100408636C (en) | 2008-08-06 |
Family
ID=36839614
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101456967B (en) * | 2009-01-05 | 2011-10-12 | 中国工程物理研究院化工材料研究所 | Method for preparing thermoplastic polyimide porous material |
| CN101645497B (en) * | 2008-08-05 | 2012-01-25 | 比亚迪股份有限公司 | Polyimide porous membrane, preparation method thereof and lithium ion battery |
| CN102585253A (en) * | 2011-12-23 | 2012-07-18 | 云南云天化股份有限公司 | Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films |
| CN101638490B (en) * | 2008-07-31 | 2012-09-12 | 比亚迪股份有限公司 | Polyimide porous membrane and preparation method and lithium ion battery thereof |
| CN101580753B (en) * | 2009-06-19 | 2012-09-26 | 大庆石油学院 | Novel polyetheretherketone self-lubricating hard wearing compound material and method for preparing same |
| CN107195252A (en) * | 2017-07-13 | 2017-09-22 | 武汉天马微电子有限公司 | Flexible display panel, display device and manufacturing method of flexible display panel |
| CN107226924A (en) * | 2017-06-28 | 2017-10-03 | 徐昌霞 | A kind of microporous foam polyimides base electro-magnetic screen composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426372B1 (en) * | 1998-07-22 | 2002-07-30 | 3M Innovative Properties Company | Method of producing porous calcined polyimide |
| JP4557409B2 (en) * | 2000-11-13 | 2010-10-06 | 日東電工株式会社 | Porous polyimide production method and porous polyimide |
| CN1321791C (en) * | 2004-03-30 | 2007-06-20 | 洛阳轴研科技股份有限公司 | Material of porous polyimide holder and molding technique |
-
2006
- 2006-02-07 CN CNB2006100381757A patent/CN100408636C/en active Active
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| CN101638490B (en) * | 2008-07-31 | 2012-09-12 | 比亚迪股份有限公司 | Polyimide porous membrane and preparation method and lithium ion battery thereof |
| CN101645497B (en) * | 2008-08-05 | 2012-01-25 | 比亚迪股份有限公司 | Polyimide porous membrane, preparation method thereof and lithium ion battery |
| CN101456967B (en) * | 2009-01-05 | 2011-10-12 | 中国工程物理研究院化工材料研究所 | Method for preparing thermoplastic polyimide porous material |
| CN101580753B (en) * | 2009-06-19 | 2012-09-26 | 大庆石油学院 | Novel polyetheretherketone self-lubricating hard wearing compound material and method for preparing same |
| CN102585253A (en) * | 2011-12-23 | 2012-07-18 | 云南云天化股份有限公司 | Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films |
| CN102585253B (en) * | 2011-12-23 | 2014-07-09 | 云南云天化股份有限公司 | Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films |
| CN107226924A (en) * | 2017-06-28 | 2017-10-03 | 徐昌霞 | A kind of microporous foam polyimides base electro-magnetic screen composite material and preparation method thereof |
| CN107195252A (en) * | 2017-07-13 | 2017-09-22 | 武汉天马微电子有限公司 | Flexible display panel, display device and manufacturing method of flexible display panel |
| CN109867891A (en) * | 2019-01-31 | 2019-06-11 | 华中科技大学鄂州工业技术研究院 | A kind of mixing prepares the clean method for preparing of high-melting-point porous material |
| CN111635551A (en) * | 2020-06-23 | 2020-09-08 | 哈尔滨工程大学 | Method for preparing polyimide open-cell foam by one-step method and product |
| CN111635551B (en) * | 2020-06-23 | 2022-04-22 | 哈尔滨工程大学 | Method for preparing polyimide open-cell foam by one-step method and product |
| CN113462010A (en) * | 2021-07-26 | 2021-10-01 | 中国科学院兰州化学物理研究所 | High-molecular polymer foam material and preparation method and application thereof |
| CN117382062A (en) * | 2023-11-20 | 2024-01-12 | 常州杰铭新材料科技有限公司 | Method for preparing cross-linked polyimide product based on cold-press sintering method |
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| CN100408636C (en) | 2008-08-06 |
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