CN106398212A - Polyimide resin composite material and preparation method thereof - Google Patents
Polyimide resin composite material and preparation method thereof Download PDFInfo
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- CN106398212A CN106398212A CN201611140029.5A CN201611140029A CN106398212A CN 106398212 A CN106398212 A CN 106398212A CN 201611140029 A CN201611140029 A CN 201611140029A CN 106398212 A CN106398212 A CN 106398212A
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- polyimide resin
- preparation
- composite material
- resin composite
- basalt fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyimide resin composite material and a preparation method thereof. The preparation method disclosed by the invention comprises the steps of carrying out modifying treatment on basalt fibers and carrying out compounding. According to the polyimide resin composite material and the preparation method thereof, the polyimide resin composite material with better basalt fiber and polyimide resin material compatibility is prepared through carrying out modifying treatment on the barium phosphate containing basalt fibers and finally carrying out coupling and compounding with polyimide resin in the presence of a coupling agent; the basalt fibers have a better reinforcing action on the polyimide resin, so that the composite material is more excellent in performance, and the popularization and application of the polyimide resin composite material in various fields are facilitated.
Description
Technical field
The present invention relates to polyimide resin composite material field and in particular to a kind of polyimide resin composite material and
Its preparation method.
Background technology
Polyimides refers to contain imide ring on main chain（-CO-NH-CO-）One birds of the same feather flock together compound, wherein to contain phthaloyl
The polymer of imine structure is mostly important.Polyimides as a kind of special engineered material, have been widely used Aeronautics and Astronautics,
The fields such as microelectronics, nanometer, liquid crystal, seperation film, laser.One of optimal high-molecular organic material of polyimides combination property,
Compared with many resin materials, polyimides has good flame resistance, and mechanical performance is high, and big using temperature range, heat-resisting quantity is good
Advantage；But polyimide resin material equally exists the defect wearing no resistance, meanwhile, its mechanical performance also needs to carry further
Height, therefore, polyimide resin material needs also exist for carrying out the composite modified process of enhancing such as toughness reinforcing, increase impact strength, expands
Its range big.Fiber-reinforced modified main employing glass fiber material to polyimide resin material and carbon fiber now
Material is modified processing, and modified effect is notable, but glass fibre and carbon fiber production cost height, environmental pollution are greatly, seriously limit
Make the application of compound polyimide resin material.
Basalt fibre is a kind of emerging novel inorganic environment-friendly and green high performance fibre material, is following China emphasis
One of four big high-performance fibers of development, it is to be aoxidized by silica, aluminum oxide, calcium oxide, iron oxide and titanium dioxide etc.
The basalt building stones of thing composition, after high-temperature fusion, are prepared from by spinning technique.Basalt continuous fiber is not only stable
Property is good, but also has electrical insulating property, anticorrosive, flame resistant, multiple excellent properties such as high temperature resistant, and, basalt fibre
The discarded object that production technology produces is few, and environmental pollution is little, can directly proceed in ecological environment after product abandonment, no any danger
Evil, thus be a kind of genuine green, environment-friendly materials.
Therefore, glass is substituted using nontoxic, pollution-free, wide material sources, excellent performance, the basalt fiber material stablized
Glass fiber and carbon fiber strengthen to polyimide resin material, from obtained from polyimide resin composite material be polyamides
The new direction of imide resin composite development.But because basalt fibre is inorganic material, and polyimide resin is high score
Sub- organic material, both compatibility extreme differences, and basalt fibre self structure and stable performance, fiber surface is smooth, live in surface
Property site is few, causes basalt fibre to be more difficult to carry out chemical bonding and machinery with polyimide resin material in modifying process
Riveted, that is, basalt fibre is to be individually present in polyimide resin material, to polyimide resin material enhancing effect not
Good, the poor-performing of polyimide resin composite material.
Content of the invention
It is an object of the invention to overcoming the inapparent defect of polyimide resin composite material performance enhancement effect, provide
A kind of polyimide resin composite material and preparation method thereof；The inventive method is by entering to the basalt fibre containing barium phosphate
Row modification, finally being carried out with polyimide resin being coupled in the presence of coupling agent, being combined, thus obtaining basalt fibre
The more preferable polyimide resin composite material with polyimide resin material compatibility, basalt fibre increases to polyimide resin
Pretend with more preferably, making this composite property more excellent, being conducive to polyimide resin composite material in the popularization of every field
Application.
In order to realize foregoing invention purpose, the invention provides a kind of preparation method of polyimide resin composite material,
Comprise the following steps：
（1）Modification：Basalt fibre is inserted in modifier A, adds modifying agent B, after reaction completely, take out basalt
Fiber, inserts and takes out after processed in dehydrating agent, then inserts in alkaline solution and carry out isomerization process, takes out after the completion of process
Dry treated basalt fiber；
（2）Compound：Treated basalt fiber and polyimide resin material, coupling agent are carried out Combined Processing, obtains polyamides sub-
Polyimide resin composite.
A kind of preparation method of above-mentioned polyimide resin composite material, the inclusion basalt wherein described in step 1 is short
One or more of fiber, basalt long fiber, continuous basalt fiber, basalt fiber cotton.
Barium phosphate is contained in described basalt fibre；Phosphate radical, the key of phosphate radical and organic group is contained in barium phosphate
The ability that connects is strong, can reduce the polarity of basalt fibre and organic material, increases the compatibility with organic material；Preferably, described
Basalt fibre contain the barium phosphate of mass percent 0.1-2.0%；Most preferably, described basalt fibre contains quality
The barium phosphate of percentage 0.3-0.8%.
Described modifier A is p-phenylenediamine solution；Solvent in described p-phenylenediamine solution be dimethyl methyl phthalein amine, two
Methylacetamide, N monomethyl adjoin pyrrolidone, adjoin one or more of smack one's lips, dimethyl sulfoxide (DMSO).
Described modifying agent B is pyromellitic acid anhydride.
Described p-phenylenediamine is 2-4 1 with the ratio of the amount of the total material of pyromellitic acid anhydride；Preferably, described right
Phenylenediamine is 31 with the ratio of the amount of the total material of pyromellitic acid anhydride.
Reaction time in modifier A with modifying agent B for the described basalt fibre is 20-40min, reaction time mistake
Short, not exclusively, the reaction time is long, overreact for reaction, and side reaction increases.
Described dehydrating agent is one of acetone, glycerine；Described dehydration treatment time is 10-30min.
Described alkaline solution is one or more of NaOH, potassium hydroxide, calcium hydroxide；At described isomerization
The reason time is 20-50min.
A kind of preparation method of above-mentioned polyimide resin composite material, the coupling agent wherein described in step 2 is silane
Coupling agent.
The consumption of described treated basalt fiber can be wanted in different application field according to polyimide resin composite material
Ask and be adjusted the 1-20% it is preferred that described treated basalt fiber consumption is polyimide resin material.
In the preparation method step 2 of described polyimide resin composite material, auxiliary agent can also be added；Described auxiliary agent includes
One or more of dispersant, antiseptic, antistatic additive, fire retardant, age resister, UV resistant agent；The kind of described auxiliary agent
Class can require to carry out specific aim adjustment interpolation according to polyimide resin composite material in different application field.
Described Combined Processing refers to enter pre-processing basalt fibre with polyimide resin material by process meanses
Row chemical bonding, makes the method that basalt fibre and polyimide resin material form unified entirety.
A kind of preparation method of polyimide resin composite material, preparation method of the present invention is first with polycondensation reaction in the Black Warrior
Rock fiber surface forms poly- phthalein amino acid, and makes it bonded with the barium phosphate on basalt fibre surface, then by dehydration and isomerization
Process forms polyimides, thus stable is coated on basalt fibre surface, dramatically increases basalt fibre and polyimides
The compatibility of resin；Finally by Combined Processing, make basalt fibre and polyimide resin carry out composite strengthening and obtain performance
More excellent polyimide resin composite material, the inventive method is simple, convenient, suitable polyimide resin composite material
Industrialization, large-scale production.
In order to realize foregoing invention purpose, further, the invention provides a kind of polyimide resin composite material；Institute
State polyimide resin composite material to prepare by above-mentioned preparation method, the composite that above-mentioned preparation method obtains
Between middle polyimide resin and basalt fibre, bonded power is strong, is not likely to produce separated, compatibility is good, and basalt fiber is to polyamides
The humidification of imide resin dramatically increases, and the performance of composite also significantly improves.
Compared with prior art, beneficial effects of the present invention：
1st, preparation method of the present invention, by the modification to basalt fibre, can dramatically increase basalt fibre and polyimides
The compatibility of resin, makes basalt fibre and polyimide resin carry out composite strengthening and obtains the more excellent polyimides of performance
Resin composite materials.
2nd, the composite property that preparation method of the present invention prepares is excellent, and method is simple, convenient, suitable polyimides
The industrialization of resin composite materials, large-scale production.
3rd, in composite of the present invention, between polyimide resin and basalt fibre, bonded power is strong, is not likely to produce phase and divides
From compatibility is good, and basalt fiber dramatically increases to the humidification of polyimide resin, and the performance of composite also significantly carries
High.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Scope for the above-mentioned theme of the present invention is only limitted to below example, all belongs to this based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）Modification：Basalt fibre containing mass percent 0.8% barium phosphate is inserted the dimethyl methyl of p-phenylenediamine
In phthalein amine aqueous solution, add pyromellitic acid anhydride, after reaction 30min, take out basalt fibre, insert and in glycerine, soak dehydration
Take out after processing 20min, then insert in sodium hydroxide solution, after reaction 35min, take out dry treated basalt fiber；
（2）Compound：Silicon by the polyimide resin material of the treated basalt fiber of 5 weight portions and 90 weight portions, 2 weight portions
Alkane coupling agent carries out Combined Processing, obtains polyimide resin composite material.
Embodiment 2
（1）Modification：Basalt fibre containing mass percent 2% barium phosphate is inserted the dimethylacetamide of p-phenylenediamine
In amine aqueous solution, add pyromellitic acid anhydride, after reaction 20min, take out basalt fibre, insert in acetone and soak at dehydration
Take out after reason 10min, then insert in potassium hydroxide solution, after reaction 50min, take out dry treated basalt fiber；
（2）Compound：Silicon by the polyimide resin material of the treated basalt fiber of 5 weight portions and 90 weight portions, 2 weight portions
Alkane coupling agent carries out Combined Processing, obtains polyimide resin composite material.
Embodiment 3
（1）Modification：Basalt fibre containing mass percent 0.1% barium phosphate is inserted the dimethyl Asia of p-phenylenediamine
In sulfolane solution, add pyromellitic acid anhydride, after reaction 40min, take out basalt fibre, insert in glycerine and soak at dehydration
Take out after reason 30min, then insert in aqua calcis, after reaction 20min, take out dry treated basalt fiber；
（2）Compound：Silicon by the polyimide resin material of the treated basalt fiber of 5 weight portions and 90 weight portions, 2 weight portions
Alkane coupling agent carries out Combined Processing, obtains polyimide resin composite material.
Embodiment 4
（1）Modification：Adjoin smack one's lips solution by what the basalt fibre containing mass percent 0.3% barium phosphate inserted p-phenylenediamine
In, add pyromellitic acid anhydride, after reaction 30min, take out basalt fibre, insert immersion processed in acetone
Take out after 20min, then insert in sodium hydroxide solution, after reaction 35min, take out dry treated basalt fiber；
（2）Compound：Silicon by the polyimide resin material of the treated basalt fiber of 5 weight portions and 90 weight portions, 2 weight portions
Alkane coupling agent carries out Combined Processing, obtains polyimide resin composite material.
Comparative example 1
（1）Modification：Conventional basalt fibre is inserted in the dimethyl methyl phthalein amine aqueous solution of p-phenylenediamine, add equal benzene four
Formic acid dianhydride, after reaction 30min, takes out basalt fibre, inserts and takes out after soaking processed 20min in glycerine, then inserts
In sodium hydroxide solution, after reaction 35min, take out dry treated basalt fiber；
（2）Compound：Silicon by the polyimide resin material of the treated basalt fiber of 5 weight portions and 90 weight portions, 2 weight portions
Alkane coupling agent carries out Combined Processing, obtains polyimide resin composite material.
Comparative example 2
Polyimide resin material by the basalt fibre containing mass percent 1.0% barium phosphate for 5 weight portions and 90 weight portions
Material, the silane coupler of 2 weight portions carry out Combined Processing, obtain polyimide resin composite material.
Comparative example 3
Silane coupler by the polyimide resin material of the conventional basalt fibre of 5 weight portions and 90 weight portions, 2 weight portions
Carry out Combined Processing, obtain polyimide resin composite material.
Polyimide resin composite material preparation-obtained in above-described embodiment 1-4 and comparative example 1-3 is carried out performance
Test experiments record experimental result, record data is as follows：（Polyimide resin：Tensile strength 116MPa, impact strength 31kJ/
m2, elongation at break 136%）
| Numbering | Polyimide resin composite material impact strength（kJ/m2） | Polyimide resin composite material tensile strength（MPa） | Polyimide resin composite material elongation at break（%） |
| Embodiment 1 | 55 | 188 | 179 |
| Embodiment 2 | 55 | 185 | 182 |
| Embodiment 3 | 53 | 187 | 176 |
| Embodiment 4 | 54 | 186 | 183 |
| Comparative example 1 | 40 | 165 | 154 |
| Comparative example 2 | 41 | 168 | 158 |
| Comparative example 3 | 34 | 136 | 146 |
Above-mentioned analysis of experimental data is understood, the polyimides tree being prepared using technical solution of the present invention in embodiment 1-4
The notch impact strength of resin composite material, tensile strength, elongation at break have and are obviously improved；And in comparative example 1 preparation method
Using basalt fibre do not contain barium phosphate, modified fiber and polyimide resin material poor compatibility, with polyimides
The chemical bonding ability of resin material, polyimide resin composite material performance significantly reduces；In comparative example 2 preparation method not
It is modified processing, less able with the chemical bonding of polyimide resin material, polyimide resin composite material performance shows
Write and reduce；Directly it is combined using conventional basalt fibre in comparative example 3 preparation method, the enhancing to polyimide resin is made
With worst.
Claims (10)
1. a kind of preparation method of polyimide resin composite material is it is characterised in that comprise the following steps：
（1）Modification：Basalt fibre is inserted in modifier A, adds modifying agent B, after reaction completely, take out basalt
Fiber, inserts and takes out after processed in dehydrating agent, then inserts in alkaline solution and carry out isomerization process, takes out after the completion of process
Dry treated basalt fiber；
（2）Compound：Treated basalt fiber and polyimide resin material, coupling agent are carried out Combined Processing, obtains polyamides sub-
Polyimide resin composite；
Barium phosphate is contained in described basalt fibre；Described modifier A is p-phenylenediamine solution；Described modifying agent B is
Pyromellitic acid anhydride.
2. preparation method according to claim 1 is it is characterised in that described basalt fibre contains mass percent
The barium phosphate of 1.0-2.0%.
3. preparation method according to claim 2 is it is characterised in that described basalt fibre contains mass percent
The barium phosphate of 0.3-0.8%.
4. preparation method according to claim 1 is it is characterised in that described dehydrating agent is one of acetone, glycerine.
5. preparation method according to claim 1 it is characterised in that described alkaline solution be NaOH, potassium hydroxide,
One or more of calcium hydroxide.
6. preparation method according to claim 1 is it is characterised in that p-phenylenediamine and pyromellitic acid anhydride in step 1
The ratio of the amount of the total material of consumption is 2-4 1.
7. preparation method according to claim 1 it is characterised in that in 1 step 1 basalt fibre modifier A with change
Property agent B in reaction time be 20-40min.
8. preparation method according to claim 1 it is characterised in that in step 1 dehydration treatment time be 10-30min.
9. preparation method according to claim 1 it is characterised in that in step 1 isomerization process time be 20-50min.
10. a kind of polyimide resin composite material is it is characterised in that described composite is any by claim 1-9
Preparation method prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611140029.5A CN106398212A (en) | 2016-12-12 | 2016-12-12 | Polyimide resin composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611140029.5A CN106398212A (en) | 2016-12-12 | 2016-12-12 | Polyimide resin composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
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| CN106398212A true CN106398212A (en) | 2017-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611140029.5A Pending CN106398212A (en) | 2016-12-12 | 2016-12-12 | Polyimide resin composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816652A (en) * | 2021-10-13 | 2021-12-21 | 西安长峰机电研究所 | Fiber-reinforced thermosetting polyimide-based composite friction material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164460A (en) * | 1990-05-30 | 1992-11-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Polyimide composite material and process for producing the same |
| CN101412849A (en) * | 2008-11-27 | 2009-04-22 | 东华大学 | Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material |
| CN101544824A (en) * | 2008-03-24 | 2009-09-30 | 中国科学院兰州化学物理研究所 | Basalt fiber-reinforced polymer-matrix self-lubricating material and preparation method thereof |
| CN104403313A (en) * | 2014-11-18 | 2015-03-11 | 上海聿衡新材料科技有限公司 | Polyimide composite material and preparation method thereof |
-
2016
- 2016-12-12 CN CN201611140029.5A patent/CN106398212A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164460A (en) * | 1990-05-30 | 1992-11-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Polyimide composite material and process for producing the same |
| CN101544824A (en) * | 2008-03-24 | 2009-09-30 | 中国科学院兰州化学物理研究所 | Basalt fiber-reinforced polymer-matrix self-lubricating material and preparation method thereof |
| CN101412849A (en) * | 2008-11-27 | 2009-04-22 | 东华大学 | Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material |
| CN104403313A (en) * | 2014-11-18 | 2015-03-11 | 上海聿衡新材料科技有限公司 | Polyimide composite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816652A (en) * | 2021-10-13 | 2021-12-21 | 西安长峰机电研究所 | Fiber-reinforced thermosetting polyimide-based composite friction material and preparation method thereof |
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Application publication date: 20170215 |