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
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Abstract
本发明公开了含氟聚酰亚胺基体树脂及其制备方法。本发明含氟聚酰亚胺基体树脂，其结构如式I。本发明以芳香族二酐、含氟取代有机二胺和反应性封端剂为原料，采用PMR方法制备的耐高温聚酰亚胺树脂基体，在树脂主链分子结构中引入含氟基团，可改善材料的加工性能和长期热氧化稳定性，在航天、航空、空间技术等高新技术领域具有潜在的应用价值。
The invention discloses a fluorine-containing polyimide matrix resin and a preparation method thereof. The structure of the fluorine-containing polyimide matrix resin of the present invention is shown in formula I. The invention uses aromatic dianhydrides, fluorine-containing substituted organic diamines and reactive end-capping agents as raw materials, adopts the high-temperature-resistant polyimide resin matrix prepared by the PMR method, and introduces fluorine-containing groups into the molecular structure of the resin main chain. It can improve the processing performance and long-term thermal oxidation stability of materials, and has potential application value in high-tech fields such as aerospace, aviation, and space technology.
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.
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| 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 |
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| 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 |
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