CN100357355C - Inorganic nano combined fiber reinforced polyimide composite material and its preparing method - Google Patents
Inorganic nano combined fiber reinforced polyimide composite material and its preparing method Download PDFInfo
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- CN100357355C CN100357355C CNB2005100120432A CN200510012043A CN100357355C CN 100357355 C CN100357355 C CN 100357355C CN B2005100120432 A CNB2005100120432 A CN B2005100120432A CN 200510012043 A CN200510012043 A CN 200510012043A CN 100357355 C CN100357355 C CN 100357355C
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Abstract
The present invention provides fiber reinforcing polyimide compound materials compounded by inorganic nano-particles and a preparing method thereof. Aliphatic homopolymerized polyimide, aromatic homopolymerized polyimide, aliphatic copolymerized polyimide and aromatic copolymerized polyimide are polymerized in situ in solution of the inorganic nano-particles or precursors of the inorganic nano-particles, and are then compounded with a fiber layer in the mode of polyamide acid solution, polyimide powder or polyimide preforming film obtained after compounded. Thus, continuous fiber reinforcing polyimide compound materials are prepared by adopting a hot moulding method. The compound materials have favorable apparent performance, and have better toughness, boundary strength and heat resistance. The matching ability between an organic phase and an inorganic phase can be improved, and polyimide is endowed with performance of low heat expandability, low hydroscopic property, high heat conductivity, etc. by the compound of the inorganic nano-particles. The present invention has the advantages of flexible operation and simple technology.
Description
Technical field
The present invention relates to a kind of inorganic nano combined fiber reinforced polyimide composite material and preparation method thereof.
Background technology
Polyimide is used as film, coating, advanced composite material resin matrix, engineering plastics and tackiness agent etc. widely with its excellent resistant of high or low temperature, favorable mechanical performance, radiation-resistant property etc.Polyimide various in style, synthetic method is flexible, can carry out monomer according to various application purposes and select, and therefore, its application aspect structured material and insulating material just constantly enlarges, and also just comes onto stage in the application of function aspects.
Fibre-reinforced composite polyimide material is owing to have excellent thermotolerance and mechanical property has been widely used in and is used as structured material in the aerospace field.And fibre-reinforced composite polyimide material is the big veriety in the high fiber-reinforced resin matrix compound material of good combination property, temperature tolerance.Its main preparation methods is a pickling process, and operating process is with the oligomer solution of polyamic acid or monomer mixture fiber impregnation to be made prepreg, then prepreg overlay is carried out mold pressing, finally makes fibre-reinforced composite polyimide material.In this method,, make that the fragility of matrix material is bigger, and then influence the actual use properties of material owing to formed the space cross-linked network.By developing new dianhydride, diamine reactant monomer and carrying out Molecular Structure Design and can improve polyimide and composite property thereof, as domestic number of patent application is 92102868.7 high toughness polyimide composite and preparation method, and application number is 92104956.0 thermoplastic polyimide composite materials and preparation method.But, on the basis of original molecular structure, utilize nanoparticle to the polyimide matrix modification, will be a kind of more convenient, more feasible method.
In recent years, it is more that relevant nanoparticle improves the research of polyimide performance.Owing to nanoparticle has special size, it is dosed in polyimide, tend to bring new performance to it.Many achievements in research show that the adding of a certain amount of inorganic nano-particle can improve mechanical property, thermotolerance, rub resistance, radiation resistance and the erosion resistance etc. of polyimide.But add-on that it should be noted that inorganic nano-particle is wanted suitably, and will notice guaranteeing that nanoparticle and polyimide have preferably the interface combine and the homodisperse problem of nanoparticle in polyimide etc.About the patent research of nanometer particle-modified polyimide is domestic nano zine oxide filled polyimide material arranged, application number is 03116357.2: foreign patent " Polycondensationcomposite composition and its manufacturing process ", the patent No. is JP2004331777.
Nanoparticle is compounded in the fibre-reinforced composite polyimide material, can give full play to the special property of nanoparticle, as high thermal conductivity, high conductivity, high adhesion, low heat expansion property, low-dielectric, agent of low hygroscopicity etc., by the performance of raising resin matrix polyimide, and then the performance of raising fibre reinforced composites.Except as traditional structured material, be endowed also that some is special functional through nano combined fiber reinforced polyimide composite material, as damping, inhale ripple, antistatic, reflection etc., the bigger effect of performance in actual applications.
Because agglomeration easily takes place in nanoparticle, therefore, the present invention prepares the even compound polyamic acid solution of nanoparticle by the coordinative role of ultra-sonic dispersion, finishing and three kinds of methods of in-situ polymerization, and then prepares fibre-reinforced composite polyimide material.At first, in certain density nanoparticle suspension, add diamines earlier, and then the adding dianhydride makes its bending reaction, synthetic homopolymerization polyimide or copolyimide; Then, again with the form of polyamic acid solution, polyimide powder or Kapton, adopt hot press method and fiber composite to prepare fibre-reinforced composite polyimide material.Because the introducing of proper amount of nano particle has improved the performance of polyimide, thereby can coordinate the Physical Match of fiber and interlaminar resin, and then improve the over-all properties of matrix material.The matrix material that adopts this method to make often has better comprehensive performance, and the thermotolerance of matrix material and mechanical property can be according to actual needs design the molecular structure of polyimide, and the range of choice of resin matrix is quite extensive.
Summary of the invention
The objective of the invention is with aliphatics homopolymerization polyimide, aromatic series homopolymerization polyimide, aliphatics copolyimide, aromatic series copolyimide as resin matrix, compound by with nanoparticle is devoted to prepare and has better processibility and stable on heating fiber reinforced polyimide composite material.
Inorganic nano combined fiber reinforced polyimide composite material of the present invention, its feature structure unit is:
In the formula,
-R-＝-O-
-Ar-＝
CH
2
n n＝1～6，
The particle diameter of inorganic nano-particle is less than 100nm, and add-on is 0.01～20wt%, is preferably 0.01～5wt%.The typical method for preparing nano combined fiber reinforced polyimide composite material:
1. adopt the method for ultra-sonic dispersion, in aprotic polar solvent, make the homodisperse aaerosol solution of nanoparticle;
2. add diamines earlier in the suspension of nanoparticle, treat to add after it dissolves fully the dianhydride of certain mole ratio again, temperature of reaction is 0～25 ℃, and the reaction times is 6～10 hours;
3. utilize nano combined polyamic acid solution to make polyimide premolding film, polyimide powder or directly use this solution impregnation to obtain the fiber prepreg;
4. with layer of fibers and polyimide premolding film or polyimide powder shop layer alternately, or directly use prepreg overlay, be positioned in the mould;
5. mould is positioned in the thermocompressor, temperature-gradient method, and near the Tg of polyimide resin, begin pressurization, and after handling through final molding temperature, the pressurize cooling.
The molar ratio of diamines and dianhydride depends on the molecular weight of the polyimide that finally obtains, and this is well-known to those skilled in the art.Step of the present invention 2. in, treat diamines and dianhydride complete reaction after, can further add single acid anhydride or monoamine end-capping reagent, the consumption of end-capping reagent is decided by formula (1),
In the formula, n
A.oAnd n
B.oThe amount of substance of representing diamines and dianhydride respectively, n
B.oThe amount of substance of expression end-capping reagent,
Single acid anhydride end-capping reagent is selected from:
The monoamine end-capping reagent is selected from:
Compound nanoparticle of the present invention is selected from; In carbon nanotube, nano silicon, nano zine oxide, nano titanium oxide, nano aluminum nitride, nano-aluminium oxide, nano barium phthalate, polynite, the clay one or more.
The reaction monomers dianhydride that the present invention uses is selected from:
Be preferably 3,3 ', 4,4 '-benzophenone dianhydride (BTDA), 3,3 ', 4, one or more in 4 '-phenyl ether dianhydride (ODPA), dihydroxyphenyl propane dianhydride (BSAA), biphenyl dianhydride (BPDA), the hexafluorodianhydride (6FDA).
The reaction monomers diamines that the present invention uses is selected from:
H
2NCH
2
nNH
2 n＝1～6，
Be preferably 3, one or more in 4 '-diaminodiphenyl oxide (ODA), benzophenone diamines (DABP), the dihydroxyphenyl propane diamines (BAPP).
The aprotic polar solvent that the present invention uses is selected from N,N-dimethylacetamide (DMAc), N, one or more in dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), the dimethyl sulfoxide (DMSO) (DMSO).
The fortifying fibre that the present invention uses is selected from: one or more in high-strength carbon fibre, high-modules carbon fibre, glass fibre, aramid fiber, boron fibre, nylon fiber, trevira, cellulose acetate, polyurethane fiber, polyacrylonitrile, polypropylene fibre, the ceramic fiber.
The present invention adopts surface treatment, ultrasonic aid dispersion, three kinds of methods of in-situ polymerization to make nanoparticle mutually compound with polyimide simultaneously.
The viscosity of the polyamic acid solution that the present invention is nano combined should be preferably 1000～3000cps less than 5000cps.
Compound nanoparticle of the present invention can directly use, and also can adopt means such as silane coupling agent, titante coupling agent, reactive monomer grafting, strong acid, highly basic etching, plasma etching that it is carried out surface activation process in advance.
The layer of fibers that the present invention uses can directly use, and also can adopt means such as silane coupling agent, titante coupling agent, soda acid etching, plasma etching, high temperature oxidation, reactive monomer grafting that activation treatment is carried out on its surface.
The nanoparticle complex method that the present invention adopts is selected from one or more in direct mixing method, interlayer interpolation, the sol-gel method.
In the nanoparticle compound polyamic acid solution of the present invention, the add-on of nanoparticle is 0.01～20wt%, is preferably 0.01～5wt%, more preferably 0.01～2wt%.
Among the present invention, the solid content of nanoparticle compound polyamic acid solution is 5～30%, is preferably 10～20wt%.
Polyimide resin matrix of the present invention is aliphatics or aromatic homopolymerization polyimide or copolyimide.
The present invention adopts the hot-imide method to prepare nano combined polyimide premolding film, adopts chemical imidization method to prepare nano combined polyimide powder.
The final imidization temperature of the polyimide preformed film that the present invention uses is 150～300 ℃, is preferably 200～250 ℃.
The final imidization temperature of the polyimide powder that the present invention uses is 200～300 ℃, is preferably 200～250 ℃.
The present invention adopts hot press method to prepare nano combined fiber reinforced polyimide composite material.
Inorganic nano combined fiber reinforced polyimide composite material of the present invention, its forming process condition is: under 100～500 ℃, be preferably 300～400 ℃, apply the pressure of 2～100MPa, be preferably 2～10MPa.
Embodiment
Embodiment 1
With ODPA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
(1) preparation of inorganic nano-particle compound polyamic acid solution.
At first, will be through the nano-TiO of Cement Composite Treated by Plasma 10min
2Particle is dissolved in the DMAc solvent, and under the situation of ultrasonic aid dispersion, mechanical stirring 2 hours obtains the homodisperse aaerosol solution of nanoparticle; Then, in containing the DMAc suspension of nanoparticle, add the diamines 3 of 0.100mol earlier, 4 '-ODA dissolves it fully; Then, in this mixing solutions, add the dianhydride ODPA of 0.0981mol, mechanical stirring make itself and 3,4 '-ODA fully reacts, and guarantees that by ice-water bath temperature of reaction is controlled at 0～25 ℃; After 8 hours abundant reaction, obtain the Mn=25000 of final polyimide, solid content is 20wt%, inorganic nano-particle compound polyamic acid solution.
(2) preparation of fibre-reinforced composite polyimide material.
At first, prepare through 200 ℃ of far infrared imidizations and have thermoplastic polyimide premolding film.The nano-TiO that contains 0.1wt% in this film
2Particle.Again preformed film and carbon fiber (T300B) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete moulding process is: directly be raised to 250 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 250 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 370 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.The Tg of this matrix material can reach 250 ℃.
Embodiment 2
With BPDA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with 3 of the BPDA of 0.0982mol and 0.100mol, 4 '-ODA is a monomer, in containing the DMAc suspension of nanoparticle, prepare the polyimide Mn=25000 that finally obtains, and inorganic nano-particle compound polyamic acid solution.Obtain the polyimide preformed film through 200 ℃ of far infrared imidizations.Dosed the carbon nanotube of 0.1wt% in this polyimide preformed film, made the polyimide preformed film have Gao Mo, high-strength and antistatic property.Preformed film and carbon fiber (M40B) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 280 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 280 ℃, begin pressurization in the temperature-rise period, pressure is 5～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 390 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.The Tg of this matrix material can reach 280 ℃.
Embodiment 3
With BTDA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with 3 of the BTDA of 0.09838mol and 0.100mol, 4 '-ODA is a monomer, in containing the DMAc suspension of nanoparticle, prepare final polyimide Mn=30000, and inorganic nano-particle compound polyamic acid solution.Obtain the polyimide preformed film through 200 ℃ of hot-imides.Dosed the nanometer AlN particle of 1.0wt% in this polyimide preformed film, made the polyimide preformed film have Gao Mo, high-strength and thermal conductivity.Preformed film and carbon fiber (T700) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 270 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 270 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 380 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.The Tg of this matrix material can reach 280 ℃.
Embodiment 4
With BSAA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with 3 of the BSAA of 0.0973mol and 0.100mol, 4 '-ODA is a monomer, PA is an end-capping reagent, in containing the DMAc suspension of nanoparticle, prepare final polyimide Mn=25000, and inorganic nano-particle compound polyamic acid solution.Obtain the polyimide preformed film through 200 ℃ of far infrared imidizations.Dosed the nanometer SiO of 1.0wt% in this polyimide preformed film
2Particle makes the polyimide preformed film have Gao Mo, high-strength and thermal conductivity.Preformed film and glass layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 230 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 230 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 350 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.The Tg of this matrix material can reach 230 ℃.
Embodiment 5
With BPDA//ODPA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with BPDA, ODPA and 3,4 '-ODA is a monomer, PA is an end-capping reagent, in containing the DMAc suspension of clay, prepare the Mn=25000 of the polyimide that finally obtains, and nanoparticle compound polyamic acid solution.Different is that ODPA joins earlier in the solution, with 3, adds BPDA after 4 '-ODA complete reaction again.The clay that organises and handle through alkyl quaternary ammonium salts (cetyl trimethylammonium bromide) that contains 1.0wt% in this polyimide preformed film.Obtain the polyimide preformed film through 200 ℃ of far infrared imidizations.Preformed film and carbon fiber (T300B) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 250 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 250 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 370 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.When the mole copolymerization ratio of BPDA and ODPA was 90/10, the Tg of this matrix material was 253 ℃.
Embodiment 6
With BPDA//BTDA/3,4 '-ODA system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with BPDA, BTDA and 3,4 '-ODA is a monomer, in containing the DMAc suspension of nanoparticle, prepares the polyimide Mn=30000 that finally obtains, and inorganic nano-particle compound polyamic acid solution.Different is that BTDA joins earlier in the solution, with 3, adds BPDA after 4 '-ODA complete reaction again.Obtain the polyimide preformed film through 200 ℃ of hot-imides.Dosed the nanometer Al of 0.5wt% in this polyimide preformed film
2O
3Particle makes the polyimide preformed film have Gao Mo, high-strength and thermal conduction characteristic.Preformed film and carbon fiber (M50J) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 270 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 270 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 380 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.When the mole copolymerization ratio of BPDA and BTDA was 20/80, the Tg of this matrix material can reach 275 ℃.
Embodiment 7
With BPDA//BSAA/3,4 '-ODA system prepares unidirectional aramid fiber enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with BPDA, BSAA and 3,4 '-ODA is a monomer, in containing the DMAc suspension of nanoparticle, prepares polyimide Mn=30000, and nanoparticle compound polyamic acid solution.Different is that BSAA joins earlier in the solution, with 3, adds BPDA after 4 '-ODA complete reaction again.Obtain the polyimide preformed film through 200 ℃ of far infrared imidizations.Dosed the nano-ZnO particle of 0.5wt% in this polyimide preformed film, made the polyimide preformed film have Gao Mo, high-strength and thermal conduction characteristic.Preformed film and aramid fiber layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 250 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 250 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 370 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional aramid fiber enhanced composite polyimide material.When the copolymerization ratio of BPDA and BSAA was 50/50, the Tg of this matrix material was 245 ℃.
Embodiment 8
With ODPA//BTDA/3,4 '-ODA is that monomer prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 1, at first with ODPA, BTDA and 3,4 '-ODA is a monomer, in containing the DMAc suspension of nanoparticle precursor, prepare the polyimide Mn=30000 that finally obtains, and inorganic nano-particle compound polyamic acid solution.Different is that ODPA joins earlier in the solution, with 3, adds BTDA after 4 '-ODA complete reaction again.Through obtaining the polyimide preformed film behind 200 ℃ of far infrared imides.The nanometer SiO that contains 1.0wt% in this polyimide preformed film
2Particle makes film have Gao Mo, high-strength and thermal conduction characteristic.Preformed film and carbon fiber (T800) layer are reduced alternately shop layer of back, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 250 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 250 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 370 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.When the copolymerization ratio of ODPA and BTDA was 40/60, the Tg of this matrix material was 260 ℃.
Embodiment 9
Prepare unidirectional polyimide fiber enhanced composite polyimide material with the BTDA/BAPP system.
(1) preparation of inorganic nano-particle compound polyamic acid solution.
At first, will be dissolved in the DMAc solvent through the nanometer AlN particle that coupling agent KH-550 handles, under the situation of ultrasonic aid dispersion, mechanical stirring 2 hours obtains the homodisperse aaerosol solution of nanoparticle; Then, in containing the DMAc suspension of nanoparticle, add the BAPP of 0.100mol, it is dissolved fully; The BTDA that in this mixing solutions, adds 0.100mol, mechanical stirring is fully reacted itself and BAPP, guarantee that by ice-water bath temperature of reaction is controlled at 0～25 ℃: after 8 hours abundant reaction, obtain nanoparticle compound polyamic acid solution, its content is the 1.0wt% of final polyimide.
(2) preparation of fibre-reinforced composite polyimide material.
After using this polyamic acid solution with the polyimide fiber dipping, obtain prepreg through 200 ℃ of far infrared imidizations.Layer is reduced alternately shop layer of back, is placed on and carries out mold pressing in the mould on thermocompressor.Concrete process is: directly be raised to 250 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 250 ℃, begin pressurization in the temperature-rise period, pressure is 5～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 330 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional polyimide fiber enhanced composite polyimide material.The Tg of this matrix material can reach 260 ℃.
Embodiment 10
Prepare unidirectional aramid fiber enhanced composite polyimide material with the ODPA/BAPP system.
According to the method identical with embodiment 9, be monomer at first with ODPA and BAPP, in containing the DMAc suspension of nanoparticle, prepare nanoparticle compound polyamic acid solution etc. mol ratio.Contain the carbon nanotube of handling through coupling agent KH-550 in this polyamic acid solution, its content is the 0.05wt% of the polyimide that finally obtains.Use this polyamic acid solution with behind the aramid fiber dipping, obtain prepreg carrying out Procuring below 200 ℃, layer is reduced alternately shop layer of back, is placed on and carries out mold pressing in the mould on thermocompressor.Concrete process is: directly be raised to 220 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 220 ℃, begin pressurization in the temperature-rise period, pressure is 5～20MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 320 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional aramid fiber enhanced composite polyimide material.The Tg of this matrix material can reach 249 ℃.
Embodiment 11
With BTDA/1, the 3-APB system prepares unidirectional aramid fiber enhanced composite polyimide material.
According to the method identical with embodiment 9, at first with BTDA and 1,3-APB is a monomer, in containing the DMAc suspension of nanoparticle, prepares nanoparticle compound polyamic acid solution etc. mol ratio.Contain the nanometer Al that handles through coupling agent KH-550 in this polyamic acid solution
2O
3Particle, its content is the 0.02wt% of the polyimide that finally obtains.Use this polyamic acid solution with behind the alumina fiber dipping, obtain prepreg carrying out Procuring below 200 ℃, layer is reduced alternately shop layer of back, is placed on and carries out mold pressing in the mould on thermocompressor.Concrete process is: directly be raised to 240 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 240 ℃, begin pressurization in the temperature-rise period, pressure is 5～20MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 350 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional alumina fiber enhanced composite polyimide material.The Tg of this matrix material can reach 240 ℃.
Embodiment 12
With 6FDA/1, the 3-APB system prepares unidirectional carbon fiber dimension enhanced composite polyimide material.
According to the method identical with embodiment 9, at first with 1 of the 6FDA of 0.10mol and 0.98mol, 3-APB is a monomer, aniline is end-capping reagent, in containing the DMAc suspension of nanoparticle, prepare the polyimide Mn=30000 that finally obtains, nanoparticle compound polyamic acid solution.Contain the nanometer AlN particle of handling through coupling agent KH-550 in this polyamic acid solution, its content is the 0.5wt% of corresponding polyimide.Different is that end-capping reagent just adds after diamines and dianhydride complete reaction.Use this polyamic acid solution with behind carbon fiber (T800) dipping, obtain prepreg carrying out Procuring below 200 ℃, layer is reduced alternately shop layer of back, is placed on and carries out mold pressing in the mould on thermocompressor.Concrete process is: directly be raised to 240 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 240 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 350 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional carbon fiber dimension enhanced composite polyimide material.The Tg of this matrix material can reach 260 ℃.
Embodiment 13
Prepare unidirectional sapphire whisker enhanced composite polyimide material with the BSAA/BAPP system.
(1) preparation of inorganic nano-particle compound polyimide powder.
At first, will be dissolved in the DMAc solvent through the nanometer AlN particle that coupling agent KH-550 handles, under the situation of ultrasonic aid dispersion, mechanical stirring 2 hours obtains the homodisperse aaerosol solution of nanoparticle; Then, in containing the NMP suspension of nanoparticle, add the BAPP of 0.100mol, it is dissolved fully; Add the BSAA of 0.100mol in this mixing solutions, mechanical stirring is fully reacted itself and BAPP, guarantees that by ice-water bath temperature of reaction is controlled at 0～25 ℃; After 8 hours abundant reaction, obtaining solid content is the nano combined polyamic acid solution of 10wt%.Behind the chemical imidization of this solution, obtain nanoparticle compound polyimide powder through acetic anhydride and triethylamine.The nanometer AlN particle that contains 0.5wt% in this polyimide powder.Again that this powder is complete to guarantee imidization through 200 ℃ back imidization.
(2) preparation of fibre-reinforced composite polyimide material.
This powder and alumina fiber layer are alternately spread layer, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 200 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 200 ℃, begin pressurization in the temperature-rise period, pressure is 5～20MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 320 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional sapphire whisker enhanced composite polyimide material.The Tg of this matrix material can reach 180 ℃.
Embodiment 14
With BSAA//PMDA/3,4 '-ODA system prepares the fibre-reinforced composite polyimide material of unidirectional SiC.
According to the method identical with embodiment 13, at first, with BSAA, PMDA and 3,4 '-ODA is a monomer, in containing the nmp solution of nanoparticle precursor, prepares the inorganic nano-particle compound polyimide powder of Mn=45000.The nano-TiO that contains 0.5wt% in this polyimide powder through coupling agent KH-550 processing
2Particle.Different is earlier BSAA to be joined 3, in the solution of 4 '-ODA, adds PMDA after the complete reaction again.This powder and SiC layer of fibers are alternately spread layer, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 220 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 220 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 320 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain the fibre-reinforced composite polyimide material of unidirectional SiC.When the copolymerization ratio of BSAA and PMDA was 20/80, the Tg of this matrix material was 280 ℃.
Embodiment 15
With ODPA//BPDA/3,4 '-ODA//4,4 '-ODA system prepares unidirectional boron fibre enhanced composite polyimide material.
According to the method identical with embodiment 13, at first, with 0.10molODPA, 0.10molBPDA, 0.10mol3,4 '-ODA and 0.10mol4,4 '-ODA is a monomer, in containing the NMP suspension of nanoparticle, prepares inorganic nano-particle compound polyimide powder.The nanometer AlN particle that contains 0.1wt% in this polyimide powder through coupling agent KH-550 processing.React in the mixing solutions of different is two kinds of dianhydrides join simultaneously two kinds of diamines.This powder and boron fibre layer are alternately spread layer, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 260 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 200 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 380 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain unidirectional boron fibre enhanced composite polyimide material.The Tg of this matrix material is 240 ℃.
Embodiment 16
With 6FDA//BPDA/4,4 '-ODA//1, the 3-APB system prepares the fibre-reinforced composite polyimide material of unidirectional SiC.
According to the method identical with embodiment 13, at first with 6FDA, BPDA and 4,4 '-ODA, 1,3-APB are monomer, in containing the NMP suspension of organic montmorillonoid, prepare Mn=40000, and inorganic nano-particle compound polyimide powder.Contain the polynite that organises and handle through alkyl quaternary ammonium salts (cetyl trimethylammonium bromide) of 1.0wt% in this polyimide powder.Different is to add 6FDA in the mixing solutions of two kinds of diamines earlier, adds BPDA after the complete reaction again.This powder and layer of fibers are alternately spread layer, be placed on and on thermocompressor, carry out mold pressing in the mould.Concrete process is: directly be raised to 220 ℃ from room temperature, be incubated one hour, exhaust 3 times; Be warmed up to 300 ℃ from 200 ℃, begin pressurization in the temperature-rise period, pressure is 2～10MPa, 300 ℃ of insulations 1 hour; Temperature is elevated to 320 ℃ again, is incubated after one hour, carry out the pressurize cooling again, obtain the fibre-reinforced composite polyimide material of unidirectional SiC.The Tg of this matrix material is 245 ℃.
Claims (13)
1. an inorganic nano combined fiber reinforced polyimide composite material is characterized in that: contain inorganic nano-particle in the described matrix material; Described inorganic nano-particle is selected from one or more in carbon nanotube, nano silicon, nano zine oxide, nano titanium oxide, nano aluminum nitride, nano-aluminium oxide, nano barium phthalate, polynite, the clay; Described fiber is selected from one or more in carbon fiber, glass fibre, aramid fiber, nylon fiber, trevira, cellulose acetate, polyurethane fiber, polyacrylonitrile, polypropylene fibre, the ceramic fiber; The particle diameter of described inorganic nano-particle is less than 100nm, and add-on is 0.01～20wt%.
2. inorganic nano combined fiber reinforced polyimide composite material as claimed in claim 1, it is characterized in that: the structural unit of described polyimide is:
In the formula,
-R-＝ --o--
-s-，-Ar-＝
CH
2
n n＝1～6。
3. one kind as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 1-2, and it is characterized in that: the add-on of described nanoparticle is 0.01～5wt%.
4. one kind as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 1-2, and it is characterized in that: described inorganic nano-particle passes through surface activation process in advance.
5. inorganic nano combined fiber reinforced polyimide composite material as claimed in claim 4, it is characterized in that: the surface activation process of described inorganic nano-particle is silane coupling agent, titante coupling agent, reactive monomer grafting, strong acid etching, highly basic etching or plasma etching treatment.
6. preparation method as each described nano combined fiber reinforced polyimide composite material among the claim 1-5, it is characterized in that: described method comprises the steps:
1. adopt in the churned mechanically while, the method for ultrasonic aid dispersion makes the homodisperse aaerosol solution of nanoparticle in aprotic polar solvent;
2. add diamines earlier in the suspension of nanoparticle, treat to add dianhydride again after it dissolves fully, temperature of reaction is 0～25 ℃, and the reaction times is 6～10 hours, obtains even heavy-gravity polyamic acid solution;
3. the polyamic acid solution that utilizes step 2. to obtain makes polyimide premolding film, polyimide powder, or directly uses this solution impregnation to obtain the fiber prepreg;
4. with layer of fibers and polyimide premolding film or powder shop layer, or directly use prepreg overlay, be positioned in the mould then;
5. it is hot-forming mould to be positioned over thermocompressor, obtains described nano combined fiber reinforced polyimide composite material;
Described inorganic nano-particle is selected from one or more in carbon nanotube, nano silicon, nano zine oxide, nano titanium oxide, nano aluminum nitride, nano-aluminium oxide, nano barium phthalate, polynite, the clay;
Described fiber is selected from one or more in carbon fiber, glass fibre, aramid fiber, nylon fiber, trevira, cellulose acetate, polyurethane fiber, polyacrylonitrile, polypropylene fibre, the ceramic fiber.
7. the preparation method of an inorganic nano combined fiber reinforced polyimide composite material as claimed in claim 6 is characterized in that: described step 2. in, treat diamines and dianhydride complete reaction after, also can add end-capping reagent.
8. the preparation method of an inorganic nano combined fiber reinforced polyimide composite material as claimed in claim 7, it is characterized in that: described end-capping reagent is selected from single acid anhydride or monoamine.
9. preparation method as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 6-8, it is characterized in that: described diamines is selected from one or more in the following diamines:
CH
2
n＝1～6 。
10. preparation method as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 6-8, it is characterized in that: described diamines is selected from: 3,3 '-diaminodiphenyl oxide (3,3 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), in the dihydroxyphenyl propane diamines (BAPP) one or more.
11. the preparation method as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 6-8, it is characterized in that: described dianhydride is selected from one or more in the following dianhydride:
12. preparation method as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 6-8, it is characterized in that: described dianhydride is selected from: 3,3 ', 4,4 '-benzophenone dianhydride (BTDA), dihydroxyphenyl propane dianhydride (BSAA) 3,3 ', 4, one or more in 4 '-phenyl ether dianhydride (ODPA).
13. the preparation method as each described inorganic nano combined fiber reinforced polyimide composite material among the claim 6-8, it is characterized in that: the nano combined polyamic acid solution viscosity that 2. step obtains is lower than 5000cps.
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