CN106398212A - Polyimide resin composite material and preparation method thereof - Google Patents
Polyimide resin composite material and preparation method thereof Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- polyimide resin
- preparation
- composite material
- resin composite
- basalt fibre
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 89
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 39
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 208000005156 Dehydration Diseases 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 238000006317 isomerization reaction Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- -1 dimethyl methyl Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241001163600 Bathylaco nigricans Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 235000021197 fiber intake Nutrition 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 |
|---|---|
| CN106398212A true CN106398212A (en) | 2017-02-15 |
Family
ID=58084956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611140029.5A Pending CN106398212A (en) | 2016-12-12 | 2016-12-12 | Polyimide resin composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106398212A (en) |
Cited By (2)
| 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 |
| CN118930915A (en) * | 2024-08-02 | 2024-11-12 | 青岛达亿星高端新材料有限公司 | Polyimide film for copper clad laminate 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 (2)
| 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 |
| CN118930915A (en) * | 2024-08-02 | 2024-11-12 | 青岛达亿星高端新材料有限公司 | Polyimide film for copper clad laminate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105504804A (en) | Halogen-free flame-retardant carbon fiber-reinforced polyamide composite material and preparation method thereof | |
| CN107033428A (en) | A kind of basalt fibre enhancing polyvinyl resin composite and preparation method thereof | |
| CN106751799B (en) | A kind of basalt fibre reinforced polyamide composite material and preparation method | |
| CN111793338B (en) | A compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and its preparation method | |
| CN106398212A (en) | Polyimide resin composite material and preparation method thereof | |
| CN106397942A (en) | Special basalt fiber for enhancing polyethylene resin material and preparation method of special basalt fiber | |
| CN109608833A (en) | A kind of high-strength anti-flaming PCT engineering plastics and preparation method thereof | |
| CN110747648B (en) | A kind of carbon fiber polyimide sizing agent and its preparation method and application | |
| CN106751445A (en) | A kind of polyether-ether-ketone enhancing composite and preparation method thereof | |
| CN115594943B (en) | Modified carbon nano tube flame-retardant reinforced epoxy resin and preparation method thereof | |
| CN113003948A (en) | Basalt fiber sizing agent, preparation method thereof and basalt fiber composite material | |
| CN106750421A (en) | A kind of phenolic resin enhancing composite and preparation method thereof | |
| CN107033592A (en) | A kind of polyimide resin enhancing composite and preparation method thereof | |
| CN106757526A (en) | A kind of polyether sulfone strengthens special basalt fibre and preparation method thereof | |
| CN106750858A (en) | A kind of polyvinyl resin Material reinforcement basalt fibre sizing agent special and preparation method thereof | |
| CN103059790A (en) | Heat-resistant, flame resistant and anti-brittle fracture modified epoxy resin adhesive and preparation method thereof | |
| CN117124666B (en) | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof | |
| CN106751306A (en) | A kind of polymethyl methacrylate enhancing composite and preparation method thereof | |
| CN106751840A (en) | A kind of polyether sulfone enhancing composite and preparation method thereof | |
| CN106746582A (en) | A kind of makrolon strengthens special basalt fibre and preparation method thereof | |
| CN106700102A (en) | Polyphenylene sulfide reinforced composite material and preparing method thereof | |
| CN115613358B (en) | Compound plant fiber flame retardant modifier and application thereof | |
| CN114957941B (en) | Functional material of modified carboxyl nitrile rubber toughened polylactic acid and preparation method thereof | |
| CN111662561B (en) | A kind of preparation method of flame-retardant, reproducible wood-plastic composite material | |
| CN106750422A (en) | A kind of polyetherimide resin composite and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170215 |