CN106393929B - Polyimide composite material and preparation method thereof - Google Patents

Polyimide composite material and preparation method thereof Download PDF

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Publication number
CN106393929B
CN106393929B CN201610799719.5A CN201610799719A CN106393929B CN 106393929 B CN106393929 B CN 106393929B CN 201610799719 A CN201610799719 A CN 201610799719A CN 106393929 B CN106393929 B CN 106393929B
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added
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CN106393929A (en
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陈亮
赵广昊
钟华春
唐柏青
程爱民
赵继辉
许建军
刘晓恒
赵继英
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Suzhou Kymler Insulation Materials Co ltd
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Suzhou Kymler Insulation Materials Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a polyimide composite material and a preparation method thereof, wherein a polyimide mixture is added into film preparation equipment to prepare a polyimide film with the thickness of 50-500 microns; then coating a modified material between the two layers of polyimide films, and heating for 15-18 minutes at 80 ℃; then heating for 8-10 minutes at 110 ℃; then heating the polyimide film for 2 minutes at 150 ℃ under a vacuum environment, and then heating the polyimide film for 5 minutes at 180 ℃ to obtain the polyimide composite material. The polyimide composite material disclosed by the invention is a material with good performance.

Description

A kind of composite polyimide material and preparation method thereof
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of preparation method of composite polyimide material.
Background technology
Polyimides has a wide range of applications as high-fire resistance resin in multiple fields.Its heat resistance and molecule knot Rigid radical in structure has a much relations, but due to the general character of organic thin film, the mechanical property of Kapton and Heat resistance is poor.The prior art generally improves the property of Kapton by way of composite reinforcing material such as fluorine-containing layer Can, there are it is obvious the problem of, the original electric property of Kapton can be caused to decline.
The content of the invention
The object of the present invention is to provide a kind of preparation method of composite polyimide material.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of composite polyimide material, comprises the following steps：
(1) by n,N-dimethylacetamide, it is delivered to molten ammonia kettle；Then diamines is added；Stir 1 it is small when, then add A collection of pyromellitic acid anhydride, when stirring 1 is small, 40 DEG C of controlling reaction temperature, then adds second batch pyromellitic acid anhydride, 5, 5 '-bis-（Triethoxy silicon substrate）- 3,3 '-bipyridyl, when stirring 1 is small, 50 DEG C of controlling reaction temperature, then adds the 3rd batch of equal benzene Tetracarboxylic acid dianhydride, when stirring 1 is small, 65 DEG C of controlling reaction temperature, adds methine succinic acid, dimethyl tin oxide, cyanate Performed polymer, prestox silsesquioxane, stirring 2 obtain polyimide mixture when small；Bisphenol A cyanate ester monomer is added to In reactor, 90~95 DEG C are heated 10~12 minutes, are warming up to 120~125 DEG C, add nonylphenol polyoxyethylene ether, tricresyl phosphate Butyl ester and 2- acrylamide-2-methylpro panesulfonic acids, acrylamide, reaction prepare cyanate performed polymer in 30~35 minutes；
(2) by butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit are added to the water to form lotion；Potassium peroxydisulfate, lithium bromide are added to the water, prepare initiator Solution；Then quality accounting is pressed, the lotion of half amount is mixed with the initiator solution of half amount, 30 are stirred in 90~105 DEG C Minute；Then under agitation, remaining lotion and remaining initiator solution are added, then is reacted 50~60 minutes, adds and fills out Material and trisphenyl glycidyl ether methylmethane, stir 20~30 minutes in 140~155 DEG C, obtain modified material；By six water nitric acid Lanthanum, nickel oxide add 4-（2- ethoxys）Mixed liquor is obtained in half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, then adds oxidation Aluminium and chitosan；Stir 4 it is small when after 150 DEG C of drying obtain solids；Solids through 550 DEG C sintering 2 it is small when after then at 800 DEG C burning Knot 4 obtains block when small, block obtains filler after pulverizing and sieving；
(3) polyimide mixture is added in membrane equipment, it is thin prepares the polyimides that thickness is 50~500 microns Film；Then modified material is coated between two layers of polyimide film, 80 DEG C are heated 15~18 minutes；Then 110 DEG C heating 8~ 10 minutes；Then under vacuum environment, polyimides composite wood is obtained then at 180 DEG C of heating within 5 minutes after being heated 2 minutes in 150 DEG C Material.
In above-mentioned steps (1), the diamines presses quality by 4,4- diaminodiphenyl ethers, phosphoric acid diamines, isophorone diamine Than 100: 3: 4 compositions.Two amine compositions of the present invention ensure the backbone structure of polyimides based on 4,4- diaminodiphenyl ethers It is regular, P elements can be introduced by phosphoric acid diamines, laid the first stone for anti-flammability, can further carried using isophorone diamine The heat resistance of high polyimides.
In above-mentioned steps (1), the equal benzene four of n,N-dimethylacetamide, diamines, first pyromellitic acid anhydride, second batch Formic acid dianhydride, 5,5 '-it is bis-（Triethoxy silicon substrate）- 3,3 '-bipyridyl, the 3rd batch of pyromellitic acid anhydride, methine succinic acid, Dimethyl tin oxide, cyanate performed polymer, the mass ratio of prestox silsesquioxane are 100: 12: 11: 1.5: 8: 0.5: 19: 1: 28∶9；Bisphenol A cyanate ester monomer, nonylphenol polyoxyethylene ether, tributyl phosphate, 2- acrylamide-2-methylpro panesulfonic acids, The mass ratio of acrylamide is 1: 0.2: 0.3: 0.05: 0.08.
In above-mentioned steps (2), the average grain diameter of the filler is 540 nanometers；4-（2- ethoxys）- 1- piperazine ethanesulfonic acids The mass concentration of half sodium salt buffer solution is 5%.
In above-mentioned steps (2), in lotion, butyl acrylate, styrene, trishydroxymethylaminomethane, polyoxyethylene nonyl phenyl second Alkene ether, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit, the mass ratio of water are 1: 0.6: 0.2: 0.15: 0.45: 0. 01 ∶0. 2∶10；In initiator solution, potassium peroxydisulfate, lithium bromide, the mass ratio of water are 1: 0.4: 5；Lotion, filler, triphenyl contracting Water glycerin ether methylmethane, the mass ratio of initiator solution are 100: 22: 12: 1.
In above-mentioned steps (2), lanthanum nitrate hexahydrate, nickel oxide, 4-（2- ethoxys）Half sodium salt of -1- piperazine ethanesulfonic acids buffers Liquid, aluminium oxide, the mass ratio of chitosan are 8: 18: 100: 28: 16.
The invention also discloses the polyimides composite wood prepared according to the preparation method of above-mentioned composite polyimide material Material.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）The present invention prepares composite polyimide material by main base material of Kapton；By in addition cyanic acid Ester performed polymer greatly improves molecule chain rigidity, and addition organic molecule adds the reactivity of cyanate, adds cyanogen The compatibility of acid esters, avoids being separated, and addition oxide material improves the activity of molecule, and when porous material is beneficial to stress Load is disperseed, and hole material is easy to be infiltrated, different beneficial to the scattered of organic matter, increase in subsequent coated processing procedure Interfacial effect between material.
（3）The composite polyimide material of the present invention is carried by reasonably designing in two layers of material of main part inter-coat The coat of filler, after the pre-heat treatment, then carries out vacuum heat, it is bonding with material of main part to not only increase coat Power and make it that coat curing degree is high, under the action of filler, coat has good cementability, heat resistance, will not Weaken the primary characteristic of Kapton.
Brief description of the drawings
Fig. 1 is product prepared by the present invention and the comparison diagram of mill run tensile strength.
Embodiment
With reference to embodiment, the invention will be further described：
In the present embodiment, diamines is by 4,4- diaminodiphenyl ethers, phosphoric acid diamines, isophorone diamine in mass ratio 100: 3: 4 compositions；DMAC N,N' dimethyl acetamide, diamines, first pyromellitic acid anhydride, second batch pyromellitic acid anhydride, 5,5 '-it is bis- （Triethoxy silicon substrate）- 3,3 '-bipyridyl, the 3rd batch of pyromellitic acid anhydride, methine succinic acid, dimethyl tin oxide, cyanogen Acid esters performed polymer, the mass ratio of prestox silsesquioxane are 100: 12: 11: 1.5: 8: 0.5: 19: 1: 28: 9；Bisphenol A-type cyanogen Acid ester monomer, nonylphenol polyoxyethylene ether, tributyl phosphate, 2- acrylamide-2-methylpro panesulfonic acids, the quality of acrylamide Than for 1: 0.2: 0.3: 0.05: 0.08；In lotion, butyl acrylate, styrene, trishydroxymethylaminomethane, polyoxyethylene nonyl phenyl Vinethene, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit, the mass ratio of water are 1: 0.6: 0.2: 0.15: 0.45: 0. 01∶0. 2∶10；In initiator solution, potassium peroxydisulfate, lithium bromide, the mass ratio of water are 1: 0.4: 5；Lotion, filler, triphenyl Glycidol ether methylmethane, the mass ratio of initiator solution are 100: 22: 12: 1；Lanthanum nitrate hexahydrate, nickel oxide, 4-（2- hydroxyl second Base）Half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, aluminium oxide, the mass ratio of chitosan are 8: 18: 100: 28: 16.
A kind of preparation method of one composite polyimide material of embodiment, comprises the following steps：
(1) by n,N-dimethylacetamide, it is delivered to molten ammonia kettle；Then diamines is added；Stir 1 it is small when, then add A collection of pyromellitic acid anhydride, when stirring 1 is small, 40 DEG C of controlling reaction temperature, then adds second batch pyromellitic acid anhydride, 5, 5 '-bis-（Triethoxy silicon substrate）- 3,3 '-bipyridyl, when stirring 1 is small, 50 DEG C of controlling reaction temperature, then adds the 3rd batch of equal benzene Tetracarboxylic acid dianhydride, when stirring 1 is small, 65 DEG C of controlling reaction temperature, adds methine succinic acid, dimethyl tin oxide, cyanate Performed polymer, prestox silsesquioxane, stirring 2 obtain polyimide mixture when small；Bisphenol A cyanate ester monomer is added to In reactor, 90 DEG C are heated 10 minutes, are warming up to 125 DEG C, add nonylphenol polyoxyethylene ether, tributyl phosphate and 2- acryloyls Amido -2- methyl propane sulfonic acids, acrylamide, reaction prepare cyanate performed polymer in 35 minutes；
(2) by butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit are added to the water to form lotion；Potassium peroxydisulfate, lithium bromide are added to the water, prepare initiator Solution；Then quality accounting is pressed, the lotion of half amount is mixed with the initiator solution of half amount, is stirred 30 minutes in 90 DEG C； Then under agitation, remaining lotion and remaining initiator solution are added, then is reacted 60 minutes, adds filler and triphenyl Glycidol ether methylmethane, stirs 20 minutes in 140 DEG C, obtains modified material；Lanthanum nitrate hexahydrate, nickel oxide addition quality is dense Spend the 4- for 5%（2- ethoxys）Obtain mixed liquor in half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, then add aluminium oxide and Chitosan；Stir 4 it is small when after 150 DEG C of drying obtain solids；Solids through 550 DEG C sintering 2 it is small when after then at 800 DEG C sintering 4 Hour obtains block, and block obtains the filler that average grain diameter is 540 nanometers after pulverizing and sieving；
(3) polyimide mixture is added in membrane equipment, prepares the Kapton that thickness is 100 microns；So Modified material is coated between two layers of polyimide film afterwards, 80 DEG C are heated 18 minutes；Then heat 8 minutes for 110 DEG C；Then it is true Under Altitude, composite polyimide material is obtained then at 180 DEG C of heating within 5 minutes after being heated 2 minutes in 150 DEG C.Table 1 is the present invention With common polyimide electrical strength data, style thickness is 100 microns.
The polyimide electrical strength data of the invention and common of table 1
Separately to common polyimide and product of the present invention, equally apply 4KV, 50HZ power-frequency voltages, test product exists Breakdown time under the conditions of this.Time is longer, then shows that resistance to aging characteristics of product are better, i.e., corona-resistance property is preferable.
The electric ageing-resistant data of the polyimide of the invention and common of table 2
Breakdown time（H）
The present invention 20
Mill run 4
It is not difficult to find out by 1 table 2 of table, polyimide prepared by the present invention, its electric durability energy higher, and it is more stable, together When greatly improved due to the introducing of inorganic material, the anti-corona performance of product, this also causes product prepared by the present invention more to grow Phase uses in the occasion of high-frequency and high-voltage.
A kind of preparation method of two composite polyimide material of embodiment, comprises the following steps：
(1) by n,N-dimethylacetamide, it is delivered to molten ammonia kettle；Then diamines is added；Stir 1 it is small when, then add A collection of pyromellitic acid anhydride, when stirring 1 is small, 40 DEG C of controlling reaction temperature, then adds second batch pyromellitic acid anhydride, 5, 5 '-bis-（Triethoxy silicon substrate）- 3,3 '-bipyridyl, when stirring 1 is small, 50 DEG C of controlling reaction temperature, then adds the 3rd batch of equal benzene Tetracarboxylic acid dianhydride, when stirring 1 is small, 65 DEG C of controlling reaction temperature, adds methine succinic acid, dimethyl tin oxide, cyanate Performed polymer, prestox silsesquioxane, stirring 2 obtain polyimide mixture when small；Bisphenol A cyanate ester monomer is added to In reactor, 95 DEG C are heated 12 minutes, are warming up to 125 DEG C, add nonylphenol polyoxyethylene ether, tributyl phosphate and 2- propylene Amide groups -2- methyl propane sulfonic acids, acrylamide, reaction prepare cyanate performed polymer in 30 minutes；
(2) by butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit are added to the water to form lotion；Potassium peroxydisulfate, lithium bromide are added to the water, prepare initiator Solution；Then quality accounting is pressed, the lotion of half amount is mixed with the initiator solution of half amount, is stirred 30 minutes in 105 DEG C； Then under agitation, remaining lotion and remaining initiator solution are added, then is reacted 60 minutes, adds filler and triphenyl Glycidol ether methylmethane, stirs 30 minutes in 155 DEG C, obtains modified material；Lanthanum nitrate hexahydrate, nickel oxide addition quality is dense Spend the 4- for 5%（2- ethoxys）Obtain mixed liquor in half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, then add aluminium oxide and Chitosan；Stir 4 it is small when after 150 DEG C of drying obtain solids；Solids through 550 DEG C sintering 2 it is small when after then at 800 DEG C sintering 4 Hour obtains block, and block obtains the filler that average grain diameter is 540 nanometers after pulverizing and sieving；
(3) polyimide mixture is added in membrane equipment, prepares the Kapton that thickness is 400 microns；So Modified material is coated between two layers of polyimide film afterwards, 80 DEG C are heated 15 minutes；Then heat 8 minutes for 110 DEG C；Then it is true Under Altitude, composite polyimide material is obtained then at 180 DEG C of heating within 5 minutes after being heated 2 minutes in 150 DEG C.
The mechanical properties data of the polyimide of the invention and common of table 3
Tensile strength MPa Elastic modulus G Pa Bending strength MPa Wear-resisting property（It is secondary）
The present invention 195 4 280 2500
Mill run 159 1.5 200 600
As can be seen from Table 3, the polyimide mechanical performance that prepared by the present invention is substantially better than mill run, especially Elasticity modulus and wear-resisting property multiple improve, this causes product of the present invention, deflection higher, beneficial to being die-cut to variously-shaped product, And repeated multiple times it can use.Product is widely used in the heater on various execution grounds.
A kind of preparation method of three composite polyimide material of embodiment, comprises the following steps：
(1) by n,N-dimethylacetamide, it is delivered to molten ammonia kettle；Then diamines is added；Stir 1 it is small when, then add A collection of pyromellitic acid anhydride, when stirring 1 is small, 40 DEG C of controlling reaction temperature, then adds second batch pyromellitic acid anhydride, 5, 5 '-bis-（Triethoxy silicon substrate）- 3,3 '-bipyridyl, when stirring 1 is small, 50 DEG C of controlling reaction temperature, then adds the 3rd batch of equal benzene Tetracarboxylic acid dianhydride, when stirring 1 is small, 65 DEG C of controlling reaction temperature, adds methine succinic acid, dimethyl tin oxide, cyanate Performed polymer, prestox silsesquioxane, stirring 2 obtain polyimide mixture when small；Bisphenol A cyanate ester monomer is added to In reactor, 95 DEG C are heated 12 minutes, are warming up to 120 DEG C, add nonylphenol polyoxyethylene ether, tributyl phosphate and 2- acryloyls Amido -2- methyl propane sulfonic acids, acrylamide, reaction prepare cyanate performed polymer in 35 minutes；
(2) by butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, Boron Trifluoride Ethylamine, uramit are added to the water to form lotion；Potassium peroxydisulfate, lithium bromide are added to the water, prepare initiator Solution；Then quality accounting is pressed, the lotion of half amount is mixed with the initiator solution of half amount, is stirred 30 minutes in 90 DEG C； Then under agitation, remaining lotion and remaining initiator solution are added, then is reacted 50 minutes, adds filler and triphenyl Glycidol ether methylmethane, stirs 20 minutes in 150 DEG C, obtains modified material；Lanthanum nitrate hexahydrate, nickel oxide addition quality is dense Spend the 4- for 5%（2- ethoxys）Obtain mixed liquor in half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, then add aluminium oxide and Chitosan；Stir 4 it is small when after 150 DEG C of drying obtain solids；Solids through 550 DEG C sintering 2 it is small when after then at 800 DEG C sintering 4 Hour obtains block, and block obtains the filler that average grain diameter is 540 nanometers after pulverizing and sieving；
(3) by polyimide mixture add membrane equipment in, prepare thickness be respectively 50 microns with 250 microns gather Imide membrane；Then it is respectively to coat modified material between 50 microns and 250 microns of two layers of polyimide film in thickness, 80 DEG C are heated 15~18 minutes；Then heat 8~10 minutes for 110 DEG C；Then under vacuum environment, after being heated 2 minutes in 150 DEG C again Composite polyimide material is obtained in 180 DEG C of heating within 5 minutes.
The product and the contrast of mill run tensile strength that attached drawing 1 is prepared for the present invention, it can be seen that tensile strength is obvious Better than common polyimide.
Composite polyimide material prepared by the present invention among two layers of polyimide film by setting modifying material layer to form； Bending strength is more than 250MPa；Heat distortion temperature is more than 400 degree；It is a kind of material of good performance.

Claims (6)

1. a kind of preparation method of composite polyimide material, comprises the following steps：
(1) by n,N-dimethylacetamide, it is delivered to molten ammonia kettle；Then diamines is added；Stir 1 it is small when, then add first Pyromellitic acid anhydride, when stirring 1 is small, 40 DEG C of controlling reaction temperature, then add second batch pyromellitic acid anhydride, 5,5 '- It is double（Triethoxy silicon substrate）- 3,3 '-bipyridyl, when stirring 1 is small, 50 DEG C of controlling reaction temperature, then adds the 3rd batch of equal benzene four Formic acid dianhydride, when stirring 1 is small, 65 DEG C of controlling reaction temperature, it is pre- to add methine succinic acid, dimethyl tin oxide, cyanate Aggressiveness, prestox silsesquioxane, stirring 2 obtain polyimide mixture when small；Bisphenol A cyanate ester monomer is added to instead Answer in device, 90~95 DEG C are heated 10~12 minutes, are warming up to 120~125 DEG C, add nonylphenol polyoxyethylene ether, tricresyl phosphate fourth Ester and 2- acrylamide-2-methylpro panesulfonic acids, acrylamide, reaction prepare cyanate performed polymer in 30~35 minutes；
(2) by butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, trifluoro Change boron mono aminoethane, uramit is added to the water to form lotion；Potassium peroxydisulfate, lithium bromide are added to the water, prepare initiator solution； Then quality accounting is pressed, the lotion of half amount is mixed with the initiator solution of half amount, is stirred 30 minutes in 90~105 DEG C； Then under agitation, remaining lotion and remaining initiator solution are added, then is reacted 50~60 minutes, adds filler and three Phenyl glycidyl ether methylmethane, stirs 20~30 minutes in 140~155 DEG C, obtains modified material；By lanthanum nitrate hexahydrate, oxygen Change nickel and add 4-（2- ethoxys）Obtain mixed liquor in half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, then add aluminium oxide and Chitosan；Stir 4 it is small when after 150 DEG C of drying obtain solids；Solids through 550 DEG C sintering 2 it is small when after then at 800 DEG C sintering 4 Hour obtains block, and block obtains filler after pulverizing and sieving；
(3) polyimide mixture is added in membrane equipment, prepares the Kapton that thickness is 50~500 microns；So Modified material is coated between two layers of polyimide film afterwards, 80 DEG C are heated 15~18 minutes；Then 8~10 points are heated for 110 DEG C Clock；Then under vacuum environment, composite polyimide material is obtained then at 180 DEG C of heating within 5 minutes after being heated 2 minutes in 150 DEG C.
2. the preparation method of composite polyimide material according to claim 1, it is characterised in that：In step (1), described two Amine is made of 4,4- diaminodiphenyl ethers, phosphoric acid diamines, isophorone diamine in mass ratio 100: 3: 4.
3. the preparation method of composite polyimide material according to claim 1, it is characterised in that：In step (1), N, N- bis- Methylacetamide, diamines, first pyromellitic acid anhydride, second batch pyromellitic acid anhydride, 5,5 '-it is bis-（Triethoxysilicane Base）- 3,3 '-bipyridyl, the 3rd batch of pyromellitic acid anhydride, methine succinic acid, dimethyl tin oxide, cyanate performed polymer, The mass ratio of prestox silsesquioxane is 100: 12: 11: 1.5: 8: 0.5: 19: 1: 28: 9；Bisphenol A cyanate ester monomer, nonyl Base phenol polyethenoxy ether, tributyl phosphate, 2- acrylamide-2-methylpro panesulfonic acids, the mass ratio of acrylamide are 1: 0.2: 0.3∶0.05∶0.08。
4. the preparation method of composite polyimide material according to claim 1, it is characterised in that：It is described to fill out in step (2) The average grain diameter of material is 540 nanometers；4-（2- ethoxys）The mass concentration of half sodium salt buffer solution of -1- piperazine ethanesulfonic acids is 5%.
5. the preparation method of composite polyimide material according to claim 1, it is characterised in that：In step (2), lotion In, butyl acrylate, styrene, trishydroxymethylaminomethane, nonylphenol polyoxyethylene ether, bicyclopentadiene, boron trifluoride list Ethamine, uramit, the mass ratio of water are 1: 0.6: 0.2: 0.15: 0.45: 0. 01: 0. 2: 10；In initiator solution, over cure Sour potassium, lithium bromide, the mass ratio of water are 1: 0.4: 5；Lotion, filler, trisphenyl glycidyl ether methylmethane, initiator solution Mass ratio is 100: 22: 12: 1.
6. the preparation method of composite polyimide material according to claim 1, it is characterised in that：In step (2), six water nitre Sour lanthanum, nickel oxide, 4-（2- ethoxys）Half sodium salt buffer solution of -1- piperazine ethanesulfonic acids, aluminium oxide, the mass ratio of chitosan are 8: 18∶100∶28∶16。
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