CN101058639A - Fluorine-containing polyimide basal body resin and preparation method thereof - Google Patents
Fluorine-containing polyimide basal body resin and preparation method thereof Download PDFInfo
- Publication number
- CN101058639A CN101058639A CN 200610076215 CN200610076215A CN101058639A CN 101058639 A CN101058639 A CN 101058639A CN 200610076215 CN200610076215 CN 200610076215 CN 200610076215 A CN200610076215 A CN 200610076215A CN 101058639 A CN101058639 A CN 101058639A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- solution
- formula
- parts
- matrix resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a fluorine polyimide base resin and making method, which is characterized by the following: adopting aromatic dianhydride, substituted organic fluorine diamine and reacted terminated agent as raw material to produce thermostable product as formula I through PMR method; leading fluorine group in the main chain molecular structure of resin; improving the manufacturing property and long-time oxidizing stability; possessing potential applying value in the high and new technological domain.
Description
Technical field
The present invention relates to a kind of polyimide resin and preparation method thereof, particularly relate to a kind of fluorinated polyimide matrix resin and preparation method thereof.
Background technology
1972, the people such as T.T.Serafini in U.S. NASA Lewis research centre (Thermally StablePolyimide from Solutions ofMonomeric Reactants, J.Appl.Polym.Sci., 1972,16:905; U.S.Patent 3,745,149) reported that high temperature resistant (316 ℃) carbon fiber of employing monomer reactant in-situ polymerization (In situ Polymerization ofMonomer Reactants) method preparation strengthens the matrix resin (PMR-15) of polyimide resin based composites.The same period, Chinese Academy of Sciences's chemistry PMR type polyimid-base resin (KH-304) of successfully having developed.Different with PMR-15; the KH-304 matrix resin has adopted nontoxic, harmless lower boiling dehydrated alcohol to replace the primary solvent of anhydrous methanol as the resins process; not only can reduce environmental pollution, protection operator ' s health, can improve the building-up properties of matrix resin simultaneously.At present, PMR-15 and KH-304 have become the main matrix resin of the anti-316 ℃ of polymer matrix composites of preparation, lightening fire resistant structural part prepared therefrom or aggregated(particle) structure spare have been widely used in many high-technology fields such as Aeronautics and Astronautics, space technology, as main duct, by-pass air duct, high speed blade, the jet valve of aircraft engine; The empennage of cruise missile, instrument compartment section, housing etc.
But PMR-15 and KH-304 polyimid-base resin also exist some shortcomings, and this has influenced the process of its practical application to a certain extent.These shortcomings mainly comprise: 1) one of principal monomer of preparation matrix resin (4,4-two amido ditanes) has the potential carinogenicity; 2) when preparing large-scale and complex parts, melt processability needs to improve; 3) impelling strength of matrix material prepared therefrom is relatively poor, requires further improvement; 4) be easy to generate fine fisssure etc. in the composite product military service process at high temperature.
1994, people such as R.H.Pater (the Thermosetting Polyimid-es.AReview in NASA Langley research centre, SAMPE Journal, v 30, n 5, Sept-Oct, 1994, p29) reported a kind of PMR type polyimid-base resin (LaRC-RP46), this matrix resin adopts 3,4 '-diamines yl diphenyl ether (3,4 '-ODA) substitutes 4 of PMR-15,4-two amido ditanes, less to environment and operator's harm, the impelling strength of prepared matrix material also obtains improvement to a certain degree.Nineteen ninety-five, people such as R.D.Vannucci (Low Cost Non-MDA Polyimide forHigh Temperature Applications, SAMPE International Symposium, 40 (1), p277) reported a kind of polyimid-base resin (AMB-21), this matrix resin adopts 2,2-pair-4-phenoxy group-4-phenyl-propane (BAPP), has good moulding processability.2000, the people such as K.C.Chuang in NASA Glenn research centre (A HighTg PMR Polyimide Composites DMBZ-15, Journal of Advanced Materials.2001,33 (4): 33) report is a kind of by 2, the PMR type polyimid-base resin of 2 '-dimethyl-benzidine (DMBZ) preparation.Polymer matrix composites prepared therefrom have high glass transition and good mechanical property.
Summary of the invention
The purpose of this invention is to provide a kind of thermosetting polyimide base resin and preparation method thereof.
Fluorinated polyimide matrix resin provided by the present invention, its structure be suc as formula I,
n＝1-10。
This fluorinated polyimide matrix resin is obtained by aromatic series tetracarboxylic dianhydride, fluorine-containing replacement diamines and reactive end-capping reagent prepared in reaction.Its preparation method comprises the steps:
A) the reactive end-capping reagent of 5-60 weight part reflux in 5-800 weight part organic solvent is generated corresponding carboxylic acid monoesters solution;
B) 100 weight part aromatic series tetracarboxylic dianhydrides reflux in 80-1800 weight part organic solvent is generated corresponding aroma family two acid diesters solution;
C) under the protection of inert gas the fluorine-containing organic diamines that is substituted with of 40-160 weight part is dissolved in the 50-1200 weight part organic solvent;
D) with above-mentioned three kinds of solution stirring reaction under protection of inert gas, obtain described fluorinated polyimide matrix resin.
Wherein, reactive end-capping reagent is the norbornylene dicarboxylic acid anhydride derivative of structure suc as formula II,
The aromatic series tetracarboxylic dianhydride is selected from 3, and 3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 4, one or more in 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides;
Fluorine-containing replacement diamines is selected from 1, one or more in two (4-amino-2-4-trifluoromethylphenopendant) benzene (6FAPB), 4,4 '-two (4-amino-5-trifluoromethyl-phenoxy group) biphenyl (6FBAB) of 4-; Its structural formula is respectively shown in formula III and formula IV:
In the above-mentioned reaction, used organic solvent comprises the mixture of anhydrous methanol, dehydrated alcohol, Virahol, propyl carbinol and arbitrary proportion thereof.
The time of step a) back flow reaction is 1-5 hour; The time of step b) back flow reaction is 1-3 hour.The temperature of step d) reaction is 5-50 ℃, and the reaction times is 2-15 hour.
According to the difference of use monomer ratio, the molecular weight of polyimide has certain variation.
The present invention with the aromatic series dianhydride, fluorine-containingly be substituted with organic diamines and reactive end-capping reagent is a raw material, adopt the fire resistant polyimide matrix resin of PMR method preparation, in the resin backbone molecular structure, introduce fluoro-containing group, can improve Drawing abillity and long term thermal oxidative stability.Matrix resin of the present invention by the aromatic series dianhydride, fluorine-containingly be substituted with organic diamines and reactive end-capping reagent prepares resin solution through heating, backflow, hybrid reaction, this resin solution has characteristics such as solids content height, viscosity is low, stability in storage is good, be suitable for impregnation of carbon fibers, glass fibre or aramid fiber etc., can be made into high-quality prepreg (band or cloth).Prepared prepreg has good composite material forming processing characteristics, low, the fine heat-resisting performance of matrix material porosity that after 50-350 ℃ heat curing process moulding, obtains, the mechanical property height, as lightweight, high-temperature-resistant structure parts or aggregated(particle) structure parts, has the potential using value at high-technology fields such as space flight, aviation, space technologies.
Embodiment
In following examples, used part all refers to weight part.
Embodiment 1,
With 3,3 ', 4,80 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) reflux in 100 parts of ethanol obtained corresponding aroma family two acid diesters solution (BTDE) in 3 hours.35 parts on end-capping reagent NA acid anhydrides reflux in 55 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 3 hours.80 parts of organic diamine monomers (6FAPB) are dissolved in 60 parts of ethanol, and stirring adds the NE and the BTDE solution of above-mentioned preparation successively after half hour; This mixed solution stirred 5 hours down at 50 ℃, obtained the solution of polyimid-base resin of solid content 47%; Its absolute viscosity (25 ℃) is 20-35mPa.s.
This resin solution steams at 60-80 ℃ of backspin removes the thick liquid that obtains behind most of solvent; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 2:
With 3,3 ', 4,121 parts of 4 '-phenyl ether tetracarboxylic dianhydrides (ODPA) reflux in 200 parts of ethanol obtained corresponding aroma family two acid diesters solution (ODPE) in 1 hour.40 parts on end-capping reagent NA acid anhydrides reflux in 55 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 5 hours.185 parts of diamine monomer 6FBAB are dissolved in 160 parts of ethanol, and stirring adds prepared NE in front and BTDE solution after half hour successively, and this mixed solution stirred 15 hours down at 5 ℃, obtains the polyimide homogeneous phase resin solution of solid content 45%.Its absolute viscosity (25 ℃) is 15-35mPa.s.
This resin solution steams at 60-80 ℃ of backspin removes the thick liquid that obtains behind most of solvent; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, mould put in the press that is preheating to 250 ℃ heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour at 270-300 ℃ of pressurization 1-10MPa, remove pressure when cooling to below 200 ℃ naturally, obtain the resin mold casting die.
Embodiment 3:
With 3,3 ', 4,400 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) reflux in 620 parts of ethanol obtained corresponding aroma family two acid diesters solution (BTDE) in 3 hours.52 parts on end-capping reagent NA acid anhydrides reflux in 64 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 2 hours.356 parts of diamine monomer 6FAPB are dissolved in 400 parts of ethanol, and stirring adds NE and the BTDE solution for preparing previously after half hour successively, and this mixed solution stirred 10 hours down at 20 ℃, obtains the polyimide homogeneous phase resin solution of solid content 43%.Its absolute viscosity (25 ℃) is 15-35mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 4:
With 3,3 ', 4,640 parts of 4 '-phenyl ether tetracarboxylic dianhydrides (BTDA) reflux in 1080 parts of methyl alcohol obtained corresponding aroma family two acid diesters solution (ODPE) in 3 hours.370 parts on end-capping reagent NA acid anhydrides reflux in 580 parts of methyl alcohol was obtained corresponding single acid monoester solution (NE) in 3 hours.795 parts of diamine monomer 6FBAB are dissolved in 900 parts of methyl alcohol, and stirring adds NE and the ODPE solution for preparing previously after half hour successively, and this mixed solution stirred 5 hours down at 40 ℃, obtains the polyimide homogeneous phase resin solution of solid content 41%.Its absolute viscosity (25 ℃) is 15-35mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 5:
With 3,70 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) reflux in 135 parts of ethanol obtained corresponding aroma family two acid diesters solution (ODPE) in 3 hours.39 parts on end-capping reagent NA acid anhydrides reflux in 54 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 3 hours.41 parts of diamine monomer 6FAPB and 35 parts of 6FBAB are dissolved in 95 parts of ethanol, add NE and the ODPE solution for preparing previously successively after stirring half hour, this mixed solution stirred 10 hours down at 30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 40%, its absolute viscosity (25 ℃) is 15-40mPa.s.
This resin solution steams at 60-80 ℃ of backspin removes the thick liquid that obtains behind most of solvent; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, mould put in the press that is preheating to 250 ℃ heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour at 270-300 ℃ of pressurization 1-10MPa, remove pressure when cooling to below 200 ℃ naturally, obtain the resin mold casting die.
Embodiment 6:
With 4,147 parts of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) reflux in 220 parts of ethanol obtained corresponding aroma family two acid diesters solution (6FDE) in 2 hours.39 parts on end-capping reagent NA acid anhydrides reflux in 50 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 1 hour.135 parts of diamine monomer 6FBAB are dissolved in 140 parts of ethanol, add NE and the 6FDE solution for preparing previously successively after stirring half hour, this solution stirred 5 hours down at 50 ℃, obtained the polyimide homogeneous phase resin solution of solid content 41%, and its absolute viscosity (25 ℃) is 20-40mPa.s.
This resin solution steams at 60-80 ℃ of backspin removes the thick liquid that obtains behind most of solvent; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 7:
With 3,3 ', 4,87 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) reflux in 110 parts of ethanol obtained corresponding aroma family two acid diesters solution (BTDE) in 3 hours, with 3,83 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) reflux in 140 parts of ethanol obtained corresponding aroma family two acid diesters solution (ODPE) in 3 hours.85 parts on end-capping reagent NA acid anhydrides reflux in 110 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 5 hours.243 parts of diamine monomer 6FBAB are dissolved in 230 parts of ethanol, add NE, BTDE and the ODPE solution for preparing previously successively after stirring half hour, this solution stirred 10 hours down at 50 ℃, obtain the polyimide homogeneous phase resin solution of solid content 46%, its absolute viscosity (25 ℃) is 25-45mPa.s.
This resin solution steams at 60-80 ℃ of backspin removes the thick liquid that obtains behind most of solvent; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 8:
With 3,3 ', 4,74 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) reflux in 110 parts of ethanol obtained corresponding aroma family two acid diesters solution (BTDE) in 3 hours, with 3,3 ', 4,134 parts of 4 '-4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) reflux in 204 parts of ethanol obtained corresponding aroma family two acid diesters solution (6FDE) in 3 hours.66 parts on end-capping reagent NA acid anhydrides reflux in 80 parts of ethanol was obtained corresponding single acid monoester solution (NE) in 5 hours.216 parts of diamine monomer 6FBAB are dissolved in 210 parts of ethanol, add NE, BTDE and the 6FDE solution for preparing previously successively after stirring half hour, this solution stirred 10 hours down at 50 ℃, obtain the polyimide homogeneous phase resin solution of solid content 43%, its absolute viscosity (25 ℃) is 20-40mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
The resulting polyimide homogeneous phase of the foregoing description resin solution, virgin resin molding and performance of composites are measured, analyzed, and the result is respectively shown in table 1-3.
The SOLUTION PROPERTIES of table 1 polyimid-base resin
| Title | Fundamental property |
| Outward appearance | Red homogeneous phase solution |
| Solid content (wt%) | 20-60 |
| Solvent | The low-boiling point alcohol kind solvent |
| 25 ℃ of viscosity | 15-400Cp |
| Package stability | 20-25 ℃: 2 months, 0 ℃: December |
The thermal characteristics of table 2 polyimide virgin resin molding
| Title | Performance index |
| Crosslinking temperature ℃ | 260-350 |
| Weightless 5% temperature ℃ | ＞470 |
| Weightless 10% temperature ℃ | ＞520 |
| Second-order transition temperature ℃ | ＞320 |
The thermal characteristics of table 3 carbon fiber reinforced matrix material
| Title | Performance index |
| Crosslinking temperature, ℃ | 270-350 |
| Weightless 5% temperature, ℃ | 480 |
| Weightless 10% temperature, ℃ | 530 |
| Second-order transition temperature, ℃ | 340 |
The result shows, thermosetting polyimide base resin solution provided by the invention has the characteristics such as solids content height, viscosity is low, storage stability is good, be suitable for impregnation of carbon fibers, glass fibre or aramid fiber etc., can be made into high-quality prepreg (band or cloth). Prepared prepreg has good composite material forming processing characteristics, low, the fine heat-resisting performance of composite porosity that after 50-350 ℃ heat curing process moulding, obtains, and mechanical property is high.
Claims (10)
1, a kind of fluorinated polyimide matrix resin, its structure be suc as formula I,
n＝1-10。
2, fluorinated polyimide matrix resin according to claim 1 is characterized in that: described fluorinated polyimide matrix resin is obtained by aromatic series tetracarboxylic dianhydride, fluorine-containing replacement diamines and reactive end-capping reagent prepared in reaction.
3, fluorinated polyimide matrix resin according to claim 2 is characterized in that:
Described reactive end-capping reagent is the norbornylene dicarboxylic acid anhydride derivative of structure suc as formula II,
Described aromatic series tetracarboxylic dianhydride is selected from 3, and 3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 4, one or more in 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides;
Described fluorine-containing replacement diamines is selected from 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4 of 4-, one or more in 4 '-two (4-amino-5-trifluoromethyl-phenoxy group) biphenyl.
4, prepare the method for the described fluorinated polyimide matrix resin of claim 1, comprise the steps:
A) the reactive end-capping reagent of 5-60 weight part reflux in 5-800 weight part organic solvent is generated corresponding carboxylic acid monoesters solution;
B) 100 weight part aromatic series tetracarboxylic dianhydrides reflux in 80-1800 weight part organic solvent is generated corresponding aroma family two acid diesters solution;
C) under the protection of inert gas the fluorine-containing organic diamines that is substituted with of 40-160 weight part is dissolved in the 50-1200 weight part organic solvent;
D) with above-mentioned three kinds of solution stirring reaction under protection of inert gas, obtain described fluorinated polyimide matrix resin.
5, method according to claim 4, it is characterized in that: described aromatic series tetracarboxylic dianhydride is selected from 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 4, one or more in 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides.
6, method according to claim 4 is characterized in that: described fluorine-containing replacement diamines is selected from 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4 of 4-, one or more in 4 '-two (4-amino-5-trifluoromethyl-phenoxy group) biphenyl.
7, method according to claim 4 is characterized in that: described reactive end-capping reagent is the norbornylene dicarboxylic acid anhydride derivative of structure suc as formula II,
8, according to the arbitrary described method of claim 4-7, it is characterized in that: described organic solvent comprises the mixture of anhydrous methanol, dehydrated alcohol, Virahol, propyl carbinol and arbitrary proportion thereof.
9, according to the arbitrary described method of claim 4-7, it is characterized in that: the time of step a) back flow reaction is 1-5 hour; The time of step b) back flow reaction is 1-3 hour.
10, according to the arbitrary described method of claim 4-7, it is characterized in that: the temperature of step d) reaction is 5-50 ℃, and the reaction times is 2-15 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610076215 CN101058639A (en) | 2006-04-19 | 2006-04-19 | Fluorine-containing polyimide basal body resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610076215 CN101058639A (en) | 2006-04-19 | 2006-04-19 | Fluorine-containing polyimide basal body resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101058639A true CN101058639A (en) | 2007-10-24 |
Family
ID=38864954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610076215 Pending CN101058639A (en) | 2006-04-19 | 2006-04-19 | Fluorine-containing polyimide basal body resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101058639A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476455A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Manufacturing method of thermoplastic composite vehicle door |
| CN102964834A (en) * | 2012-11-22 | 2013-03-13 | 中国科学院化学研究所 | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof |
| CN103450796A (en) * | 2012-05-31 | 2013-12-18 | 上海三电贝洱汽车空调有限公司 | Sliding film on surface of compressor sliding part and formation method thereof |
| CN103772871A (en) * | 2013-12-20 | 2014-05-07 | 苏州市万泰真空炉研究所有限公司 | Preparation method of novel composite polyimide foamed plastic |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN104072770A (en) * | 2014-06-30 | 2014-10-01 | 自贡中天胜新材料科技有限公司 | Foamed fluorine-containing polyimide and preparation method of foam thereof |
| CN105061764A (en) * | 2015-09-02 | 2015-11-18 | 中国科学院化学研究所 | Thermosetting polyamide resin and composite laminated plate thereof, and preparation method and application thereof |
| CN106450445A (en) * | 2016-10-14 | 2017-02-22 | 华南理工大学 | Fluorine-containing polyimide polymer electrolyte as well as preparation method and application thereof |
| CN108395535A (en) * | 2018-04-03 | 2018-08-14 | 上海市合成树脂研究所有限公司 | A kind of imido preparation method of hot polymerization for laminated product |
| CN110591132A (en) * | 2019-08-30 | 2019-12-20 | 德州联合拓普复合材料科技有限公司 | Carbon fiber prepreg |
-
2006
- 2006-04-19 CN CN 200610076215 patent/CN101058639A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476455A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Manufacturing method of thermoplastic composite vehicle door |
| CN102476455B (en) * | 2010-11-29 | 2015-07-08 | 上海杰事杰新材料(集团)股份有限公司 | Manufacturing method of thermoplastic composite vehicle door |
| CN103450796A (en) * | 2012-05-31 | 2013-12-18 | 上海三电贝洱汽车空调有限公司 | Sliding film on surface of compressor sliding part and formation method thereof |
| CN102964834B (en) * | 2012-11-22 | 2015-03-11 | 中国科学院化学研究所 | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof |
| CN102964834A (en) * | 2012-11-22 | 2013-03-13 | 中国科学院化学研究所 | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof |
| CN103772871A (en) * | 2013-12-20 | 2014-05-07 | 苏州市万泰真空炉研究所有限公司 | Preparation method of novel composite polyimide foamed plastic |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN103980489B (en) * | 2014-04-30 | 2018-08-31 | 中国科学院化学研究所 | A kind of low melt viscosity thermoplastic polyimide material and its 3D printing forming method |
| CN104072770A (en) * | 2014-06-30 | 2014-10-01 | 自贡中天胜新材料科技有限公司 | Foamed fluorine-containing polyimide and preparation method of foam thereof |
| CN104072770B (en) * | 2014-06-30 | 2016-04-20 | 自贡中天胜新材料科技有限公司 | A kind of foaming fluorinated polyimide and foam preparation processes thereof |
| CN105061764A (en) * | 2015-09-02 | 2015-11-18 | 中国科学院化学研究所 | Thermosetting polyamide resin and composite laminated plate thereof, and preparation method and application thereof |
| CN106450445A (en) * | 2016-10-14 | 2017-02-22 | 华南理工大学 | Fluorine-containing polyimide polymer electrolyte as well as preparation method and application thereof |
| CN108395535A (en) * | 2018-04-03 | 2018-08-14 | 上海市合成树脂研究所有限公司 | A kind of imido preparation method of hot polymerization for laminated product |
| CN110591132A (en) * | 2019-08-30 | 2019-12-20 | 德州联合拓普复合材料科技有限公司 | Carbon fiber prepreg |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101058639A (en) | Fluorine-containing polyimide basal body resin and preparation method thereof | |
| CN1320060C (en) | Short-fiber reinforced polyimide composite material, and its preparing method and use | |
| CN101190968A (en) | Polyimide resin and preparation method thereof | |
| AU2006331934B2 (en) | Two-stage cure polyimide oligomers | |
| CN101654518B (en) | Thermosetting polyimide resin and preparation method and application thereof | |
| CN107011657B (en) | A kind of high-ductility bimaleimide resin and its preparation method and application | |
| CN101068867A (en) | Nanoparticle silica filled benzoxazine compositions | |
| EP1734069B1 (en) | Composite material | |
| CN1884376A (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| CN105367793A (en) | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof | |
| EP3131955A1 (en) | Method for a composite material impregnated with thermoplastic polymer, obtained from a prepolymer and a chain extender | |
| CN1244879A (en) | Polyimides having high Tg, high TOS and low moisture regain | |
| CN103304999A (en) | Cyanate ester/metal aluminum or titanium-containing silsesquioxane composition | |
| CN112194900A (en) | Silicon rubber mold for integral molding of composite skirt and preparation method thereof | |
| CN1269873C (en) | Thermosetting polyimide matrix resin, preparation and use thereof | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN1123589C (en) | Thermosetting polyimide base resin and its prepn. | |
| Wang et al. | A novel condensation–addition-type phenolic resin (MPN): synthesis, characterization and evaluation as matrix of composites | |
| CN108395696B (en) | Hollow microsphere composite modified thermosetting polyimide material and preparation method thereof | |
| Yang et al. | Polyimide matrices for carbon fiber composites | |
| RU2585638C1 (en) | Epoxy binder, prepreg based thereon and article made therefrom | |
| CN114369215B (en) | Hybrid phenolic resin, synthetic method thereof and fiber/hybrid phenolic resin composite material | |
| CN1978487A (en) | 4-styryl-3-Trifluoro methyl benzeneamine and its polyimide resin, and its preparing method | |
| JP5610335B2 (en) | Method for producing fiber-reinforced polyimide material with improved mechanical strength | |
| CN101735458B (en) | Low melt viscosity ethylene rhodanate/bimaleimide resin, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |