CN109439208A - A kind of high toughness polyimide material and its application - Google Patents

A kind of high toughness polyimide material and its application Download PDF

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Publication number
CN109439208A
CN109439208A CN201811131928.8A CN201811131928A CN109439208A CN 109439208 A CN109439208 A CN 109439208A CN 201811131928 A CN201811131928 A CN 201811131928A CN 109439208 A CN109439208 A CN 109439208A
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minutes
high toughness
polyimide material
added
acid
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赵继英
赵广昊
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Suzhou Caim insulation materials Co., Ltd.
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Nantong Kai Ying Thin Film Technique Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Abstract

The invention discloses a kind of high toughness polyimide material and its applications, and adhesives is coated on Kapton surface, and 90 DEG C are heated 5~8 minutes, and the Kapton with adhesive layer is obtained；Adhesives is coated on toughening layer surface, 60 DEG C are heated 10~15 minutes, and the toughening layer with adhesive layer is obtained；Then the compound Kapton with adhesive layer obtains high toughness polyimide material with the toughening layer for having adhesive layer, hot pressing；The adhesive layer is between Kapton and toughening layer.The present invention is compound using modified olefin layer progress on the basis of Kapton, by the reasonable molecular modification object of compatibility, improves the toughness and processability of polyimides, while keeping the heat resistance of entire material, has expanded the application of polyimides.

Description

A kind of high toughness polyimide material and its application
The present invention is entitled a kind of high toughness polyimide material and preparation method thereof, application No. is 2016106238760, the applying date is the divisional application of the patent application on the 2nd of August in 2016, belongs to product and application obscure portions.
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of high toughness polyimide material and its application.
Background technique
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 much relations, while also in that the largely presence of rigid radical, leads to the tough of polyimide material Property is very poor, has larger impact to its processability and application performance.The preparation of macromolecular fibre generally comprises material modification and obtains Modifier, then carry out spinning；Or modifier mixed again with other additives after carry out spinning again；Olefin(e) fibre yield is larger, Cost is very low, but due to its strong inert, resistance to heat differential, and it is not used as compound polyimide material.Therefore it needs to be modified it, Using new technology, high toughness polyimide material is prepared on olefin basis to expand its application.
Summary of the invention
The object of the present invention is to provide a kind of high toughness polyimide materials and preparation method thereof, have excellent toughness, Good heat resistance is still kept simultaneously.
To achieve the above object of the invention, the technical solution adopted by the present invention is that:
A kind of preparation method of high toughness polyimide material, comprising the following steps:
(1) bisphenol A cyanate ester monomer is added in reactor, 90~95 DEG C are reacted 10~12 minutes, and three contractings are added Water glyceryl cyamelide ester monomer is warming up to 120~125 DEG C, and nonylphenol polyoxyethylene ether and zinc titanate, reaction 50 is added Prepare cyanate performed polymer within~65 minutes；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer are uniformly mixed, It is processed through screw rod melting extrusion, olefin particles is prepared；Then by olefin particles and dimethyl tin oxide, 2- acrylamide Base -2- methyl propane sulfonic acid, 3-acetylaminoaniline are uniformly mixed, and obtain compositions of olefines, then obtain alkene fibre through melt spinning Dimension；By polytetrafluoroethylparticle particle and five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (three ethoxies Base silicon substrate) -3, melt spinning method is used after the mixing of 3 '-bipyridyls, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, gather Tetrafluoroethylene fiber is blended by 20: 1 mass ratio progress, obtains toughening layer；
(2) aluminum phosphate and talcum powder, yttrium oxide are sintered 25~35 minutes at 800 DEG C after mixing, are then comminuted into The powder that average grain diameter is 250 nanometers；It disperses the powder into 30 times of powder weight of ethyl alcohol, powder weight 0.5% is added Isomerous tridecanol polyoxyethylene ether stirs 85~95 minutes in 50 DEG C, the P-hydroxybenzoic acid of powder weight 0.5% is then added Methyl esters stirs 25~35 minutes, last drying to obtain filler；4- (2- is added in pentaerythritol tetraacrylate, polyethylene glycol Ethoxy) in sodium salt buffer, filler and phthalic acid two is added after stirring 45~55 minutes in -1- piperazine ethanesulfonic acid half Ethylene oxidic ester is added trifluoromethanesulfonic acid lanthanum and butyl acrylate after stirring 65~75 minutes in 80 DEG C, it is small to continue stirring 2~3 When, obtain adhesives；
(3) adhesives is coated on Kapton surface, 90 DEG C are heated 5~8 minutes, are obtained with adhesive layer Kapton；Adhesives is coated on toughening layer surface, 60 DEG C are heated 10~15 minutes, and the increasing with adhesive layer is obtained Tough layer；Then the compound Kapton with adhesive layer obtains high tenacity polyamides with the toughening layer for having adhesive layer, hot pressing Imines material；The adhesive layer is between Kapton and toughening layer.
In the present invention, in step (1), the extrusion temperature of screw rod melting extrusion processing is 180~200 DEG C, screw speed control 150~175 revs/min are made as, residence time of the material in screw rod is 2~3 minutes；Melt spinning obtains temperature when olefin(e) fibre It is 190~200 DEG C, spinning speed is 400~600 ms/min；Melt spinning obtain when polytetrafluoroethylene fibre temperature be 310~ 320 DEG C, spinning speed is 600~700 ms/min.
In the present invention, in step (1), bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, nonyl The mass ratio of base phenol polyethenoxy ether and zinc titanate is 1: 0.8: 0.4: 0.02；Polyethylene, polypropylene, methine succinic acid and cyanogen The mass ratio of acid esters performed polymer is 1: 1.1: 0.2: 0.3；Olefin particles, dimethyl tin oxide, 2- acrylamido -2- methyl-prop Sulfonic acid, 3-acetylaminoaniline mass ratio be 1: 0.0005: 0.2: 0.08；Polytetrafluoroethylparticle particle, five nitric hydrate bismuths, three Aoxidize two antimony, uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls mass ratio be 1: 0.009 ∶0.18∶0.2∶0.3∶0.12。
In the present invention, in step (2), aluminum phosphate, talcum powder, yttrium oxide mass ratio be 5: 1: 0.01；Pentaerythrite four Acrylate, polyethylene glycol, half sodium salt buffer of 4- (2- ethoxy) -1- piperazine ethanesulfonic acid, filler, phthalic acid two contract Water glyceride, trifluoromethanesulfonic acid lanthanum, butyl acrylate mass ratio be 1: 0.5: 6: 0.2: 0.4: 0.001: 0.6；4- (2- hydroxyl second Base) -1- piperazine ethanesulfonic acid half sodium salt buffer mass concentration be 2%.
In the present invention, in step (3), the pressure of the hot pressing is 1.2MPa, and temperature is 125 DEG C, and the time is 4~6 minutes. Apparent polymerization reaction occurs under this hot pressing condition for adhesive layer, so that Kapton is firmly compound with toughening layer Together, become whole, so that Kapton and toughening layer are born collectively as carrier when heated, stress, avoid Overall performance is caused to decline because one of them is weaker.
The invention also discloses the high tenacity polyamides prepared according to the preparation method of above-mentioned high toughness polyimide material is sub- Amine material, wherein the Kapton with a thickness of 20~100 microns；The toughening layer with a thickness of 8~25 microns.This The method of invention is applicable in the Kapton of most of specification, is designed in this way on the basis for improving polyimides mechanical property On, the rigidity and heat resistance that still its can be kept excellent.
Further, the invention also discloses above-mentioned high toughness polyimide materials to prepare answering in polyimides plate With.Can be or compound with other polymers layer with several layers of high toughness polyimide Material claddings, obtain polyimides plate.
In the present invention, surface treatment with organic compound to inorganic material, can be enhanced inorganic matter and remaining it is organic at The compatibility divided；The fine dispersion of interface interaction and nanoparticle between nanoparticle and matrix of the present invention is to improve composite wood The key factor of the mechanical property of material, while organic compound also needs to have preferable reactivity with other adding ingredients, it can To form macromolecular chain structure, the low resistance to heat problem of existing surface treating agent is avoided；The inorganic rigid nanoparticle of high-modulus Addition improves whole modulus and stress peptizaiton, and the concentration of stress caused by nanoparticle leads to base when due to material stress Body produces shear yielding, to improve the overall flexibility of material, in addition the selection of inorganic particle size is to polymer material Strengthening and Toughening also have certain facilitation.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
(1) present invention is used using polyethylene, polypropylene as primary raw material, and by adding reasonable material, melt spinning is obtained To olefin(e) fibre, solve the problems, such as that existing olefin(e) fibre processability is poor, mechanical strength is low, especially modified alkene is fine Dimension has certain heat resistance, solves the problems, such as that prior art olefin polymer heat resistance is poor；Cyanate performed polymer is made Grain, improves the strand rigidity of olefin polymer, improves its heat resistance, can increase alkene and cyanogen using methine succinic acid The compatibility of acid esters performed polymer proposes the stability of entire polymer；Recycle small molecule modifier in melt-spun to olefin-modified, Its heat resistance and resistance to ag(e)ing can be improved on the basis of keeping alkene excellent mechanical performances.
(2) present invention greatly improves the wearability of polyimide material using polytetrafluoroethylene fibre, improves together The heat resistance of the low-melting-point resins such as polypropylene；Utilize adding ingredient on the one hand in fibrillated polytetrafluoroethylene in melt spinning process simultaneously Dimension table face forms micropore, on the one hand increases its surface-active, solves existing polytetrafluoroethylene fibre strong inert, can not be with it The compatible problem of his fiber, adhesive layer can penetrate into micropore, improve the combination of entire toughening layer and Kapton Power avoids the prior art and is easy to appear the defect for mutually separating and material overall performance being caused to decline.
(3) adhesives of the invention has the very strong compound of response type by reasonably designing；By respectively to poly- Imide membrane and toughening layer coating, the pre-heat treatment, improve the distribution consistency degree and initial reaction degree of adhesive layer, are passing through Hot pressing, two layers of adhesive layer is compound, entirety can be reacted between adhesive layer, it can also be thin with toughening layer and polyimides Film forms good bonding, to improve the mechanical property and heat resistance of composite material entirety.
(4) present invention is compound using modified olefin layer progress on the basis of Kapton, reasonable by compatibility Molecular modification object, improve the toughness and processability of polyimides, while keeping the heat resistance of entire material, expanded poly- Imido application.
Specific embodiment
The present invention will be further described below with reference to examples:
A kind of preparation method of the high toughness polyimide material of embodiment one, comprising the following steps:
(1) bisphenol A cyanate ester monomer is added in reactor, 95 DEG C are reacted 12 minutes, and triglycidyl group is added Cyamelide ester monomer is warming up to 125 DEG C, and nonylphenol polyoxyethylene ether and zinc titanate is added, and reaction prepares cyanic acid in 50 minutes Ester performed polymer；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer are uniformly mixed, added through screw rod melting extrusion Olefin particles are prepared in work；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, Amino acetanilide is uniformly mixed, and obtains compositions of olefines, then obtain olefin(e) fibre through melt spinning；By polytetrafluoroethylparticle particle With five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls Melt spinning method is used after mixing, and polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre by 20: 1 Mass ratio progress is blended, obtains toughening layer；The extrusion temperature of screw rod melting extrusion processing is 180~200 DEG C, screw speed control It is 150~175 revs/min, residence time of the material in screw rod is 2~3 minutes；Temperature is when melt spinning obtains olefin(e) fibre 190~200 DEG C, spinning speed is 600 ms/min；It is 310~320 DEG C that melt spinning, which obtains temperature when polytetrafluoroethylene fibre, is spun Silk speed is 600 ms/min；Bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, polyoxyethylene nonyl phenyl second The mass ratio of alkene ether and zinc titanate is 1: 0.8: 0.4: 0.02；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer Mass ratio be 1: 1.1: 0.2: 0.3；Olefin particles, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, ammonia The mass ratio of base antifebrin is 1: 0.0005: 0.2: 0.08；Polytetrafluoroethylparticle particle, five nitric hydrate bismuths, antimony oxide, Uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls mass ratio be 1: 0.009: 0.18: 0.2 :0.3:0.12；
(2) aluminum phosphate that mass ratio is 5: 1: 0.01 is sintered 25 points at 800 DEG C after mixing with talcum powder, yttrium oxide Clock is then comminuted into the powder that average grain diameter is 250 nanometers；It disperses the powder into 30 times of powder weight of ethyl alcohol, powder is added The isomerous tridecanol polyoxyethylene ether of last weight 0.5% stirs 95 minutes in 50 DEG C, pair of powder weight 0.5% is then added Methyl hydroxybenzoate stirs 35 minutes, last drying to obtain filler；Pentaerythritol tetraacrylate, polyethylene glycol are added Enter in the half sodium salt buffer of 4- (2- ethoxy) -1- piperazine ethanesulfonic acid that mass concentration is 2%, stirring is added after 55 minutes and fills out Trifluoromethanesulfonic acid lanthanum and butyl acrylate is added after stirring 65 minutes in 80 DEG C in material and o-phthalic acid diglycidyl ester, Continue stirring 2 hours, obtains adhesives；Pentaerythritol tetraacrylate, polyethylene glycol, 4- (2- ethoxy) -1- piperazine second The quality of half sodium salt buffer of alkyl sulfonic acid, filler, o-phthalic acid diglycidyl ester, trifluoromethanesulfonic acid lanthanum, butyl acrylate Than being 1: 0.5: 6: 0.2: 0.4: 0.001: 0.6；
(3) adhesives is coated on Kapton surface, 90 DEG C are heated 8 minutes, are obtained poly- with adhesive layer Imide membrane；Adhesives is coated on toughening layer surface, 60 DEG C are heated 10 minutes, and the toughening layer with adhesive layer is obtained； Then the compound Kapton with adhesive layer obtains high toughness polyimide material with the toughening layer for having adhesive layer, hot pressing Material；Two adhesive layers are opposite；The pressure of hot pressing is 1.2MPa, and temperature is 125 DEG C, and the time is 6 minutes.
A kind of preparation method of the high toughness polyimide material of embodiment two, comprising the following steps:
(1) bisphenol A cyanate ester monomer is added in reactor, 90 DEG C are reacted 10 minutes, and triglycidyl group is added Cyamelide ester monomer is warming up to 125 DEG C, and nonylphenol polyoxyethylene ether and zinc titanate is added, and reaction prepares cyanic acid in 65 minutes Ester performed polymer；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer are uniformly mixed, added through screw rod melting extrusion Olefin particles are prepared in work；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, Amino acetanilide is uniformly mixed, and obtains compositions of olefines, then obtain olefin(e) fibre through melt spinning；By polytetrafluoroethylparticle particle With five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls Melt spinning method is used after mixing, and polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre by 20: 1 Mass ratio progress is blended, obtains toughening layer；The extrusion temperature of screw rod melting extrusion processing is 180~200 DEG C, screw speed control It is 150~175 revs/min, residence time of the material in screw rod is 2~3 minutes；Temperature is when melt spinning obtains olefin(e) fibre 190~200 DEG C, spinning speed is 400 ms/min；It is 310~320 DEG C that melt spinning, which obtains temperature when polytetrafluoroethylene fibre, is spun Silk speed is 700 ms/min；Bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, polyoxyethylene nonyl phenyl second The mass ratio of alkene ether and zinc titanate is 1: 0.8: 0.4: 0.02；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer Mass ratio be 1: 1.1: 0.2: 0.3；Olefin particles, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, ammonia The mass ratio of base antifebrin is 1: 0.0005: 0.2: 0.08；Polytetrafluoroethylparticle particle, five nitric hydrate bismuths, antimony oxide, Uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls mass ratio be 1: 0.009: 0.18: 0.2 :0.3:0.12；
(2) aluminum phosphate that mass ratio is 5: 1: 0.01 is sintered 35 points at 800 DEG C after mixing with talcum powder, yttrium oxide Clock is then comminuted into the powder that average grain diameter is 250 nanometers；It disperses the powder into 30 times of powder weight of ethyl alcohol, powder is added The isomerous tridecanol polyoxyethylene ether of last weight 0.5% stirs 95 minutes in 50 DEG C, pair of powder weight 0.5% is then added Methyl hydroxybenzoate stirs 35 minutes, last drying to obtain filler；Pentaerythritol tetraacrylate, polyethylene glycol are added Enter in the half sodium salt buffer of 4- (2- ethoxy) -1- piperazine ethanesulfonic acid that mass concentration is 2%, stirring is added after 55 minutes and fills out Trifluoromethanesulfonic acid lanthanum and butyl acrylate is added after stirring 65 minutes in 80 DEG C in material and o-phthalic acid diglycidyl ester, Continue stirring 3 hours, obtains adhesives；Pentaerythritol tetraacrylate, polyethylene glycol, 4- (2- ethoxy) -1- piperazine second The quality of half sodium salt buffer of alkyl sulfonic acid, filler, o-phthalic acid diglycidyl ester, trifluoromethanesulfonic acid lanthanum, butyl acrylate Than being 1: 0.5: 6: 0.2: 0.4: 0.001: 0.6；
(3) adhesives is coated on Kapton surface, 90 DEG C are heated 8 minutes, are obtained poly- with adhesive layer Imide membrane；Adhesives is coated on toughening layer surface, 60 DEG C are heated 10 minutes, and the toughening layer with adhesive layer is obtained； Then the compound Kapton with adhesive layer obtains high toughness polyimide material with the toughening layer for having adhesive layer, hot pressing Material；Two adhesive layers are opposite；The pressure of hot pressing is 1.2MPa, and temperature is 125 DEG C, and the time is 6 minutes.
A kind of preparation method of the high toughness polyimide material of embodiment three, comprising the following steps:
(1) bisphenol A cyanate ester monomer is added in reactor, 92 DEG C are reacted 10 minutes, and triglycidyl group is added Cyamelide ester monomer is warming up to 122 DEG C, and nonylphenol polyoxyethylene ether and zinc titanate is added, and reaction prepares cyanic acid in 58 minutes Ester performed polymer；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer are uniformly mixed, added through screw rod melting extrusion Olefin particles are prepared in work；Then by olefin particles and dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, Amino acetanilide is uniformly mixed, and obtains compositions of olefines, then obtain olefin(e) fibre through melt spinning；By polytetrafluoroethylparticle particle With five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls Melt spinning method is used after mixing, and polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoroethylene fibre by 20: 1 Mass ratio progress is blended, obtains toughening layer；The extrusion temperature of screw rod melting extrusion processing is 180~200 DEG C, screw speed control It is 150~175 revs/min, residence time of the material in screw rod is 2~3 minutes；Temperature is when melt spinning obtains olefin(e) fibre 190~200 DEG C, spinning speed is 500 ms/min；It is 310~320 DEG C that melt spinning, which obtains temperature when polytetrafluoroethylene fibre, is spun Silk speed is 700 ms/min；Bisphenol A cyanate ester monomer, triglycidyl group cyamelide ester monomer, polyoxyethylene nonyl phenyl second The mass ratio of alkene ether and zinc titanate is 1: 0.8: 0.4: 0.02；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer Mass ratio be 1: 1.1: 0.2: 0.3；Olefin particles, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, ammonia The mass ratio of base antifebrin is 1: 0.0005: 0.2: 0.08；Polytetrafluoroethylparticle particle, five nitric hydrate bismuths, antimony oxide, Uramit, acrylamide, 5,5 '-bis- (triethoxy silicon substrates) -3,3 '-bipyridyls mass ratio be 1: 0.009: 0.18: 0.2 :0.3:0.12；
(2) aluminum phosphate that mass ratio is 5: 1: 0.01 is sintered 28 points at 800 DEG C after mixing with talcum powder, yttrium oxide Clock is then comminuted into the powder that average grain diameter is 250 nanometers；It disperses the powder into 30 times of powder weight of ethyl alcohol, powder is added The isomerous tridecanol polyoxyethylene ether of last weight 0.5% stirs 88 minutes in 50 DEG C, pair of powder weight 0.5% is then added Methyl hydroxybenzoate stirs 28 minutes, last drying to obtain filler；Pentaerythritol tetraacrylate, polyethylene glycol are added Enter in the half sodium salt buffer of 4- (2- ethoxy) -1- piperazine ethanesulfonic acid that mass concentration is 2%, stirring is added after 48 minutes and fills out Trifluoromethanesulfonic acid lanthanum and butyl acrylate is added after stirring 68 minutes in 80 DEG C in material and o-phthalic acid diglycidyl ester, Continue stirring 2.5 hours, obtains adhesives；Pentaerythritol tetraacrylate, polyethylene glycol, 4- (2- ethoxy) -1- piperazine The matter of half sodium salt buffer of ethane sulfonic acid, filler, o-phthalic acid diglycidyl ester, trifluoromethanesulfonic acid lanthanum, butyl acrylate Amount is than being 1: 0.5: 6: 0.2: 0.4: 0.001: 0.6；
(3) adhesives is coated on Kapton surface, 90 DEG C are heated 6 minutes, are obtained poly- with adhesive layer Imide membrane；Adhesives is coated on toughening layer surface, 60 DEG C are heated 13 minutes, and the toughening layer with adhesive layer is obtained； Then the compound Kapton with adhesive layer obtains high toughness polyimide material with the toughening layer for having adhesive layer, hot pressing Material；Two adhesive layers are opposite；The pressure of hot pressing is 1.2MPa, and temperature is 125 DEG C, and the time is 5 minutes.
The said goods are tested, the results are shown in Table 1.
1 embodiment product test result of table

Claims (9)

1. a kind of high toughness polyimide material, which is characterized in that the preparation method of the high toughness polyimide material includes Following steps:
(1) bisphenol A cyanate ester monomer is added in reactor, 90~95 DEG C are reacted 10~12 minutes, and it is sweet that three shrinks are added Oil base cyamelide ester monomer is warming up to 120~125 DEG C, and nonylphenol polyoxyethylene ether and zinc titanate, reaction 50~65 is added Minute prepares cyanate performed polymer；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer are uniformly mixed, through spiral shell Bar melting extrusion processing, is prepared olefin particles；Then by olefin particles and dimethyl tin oxide, 2- acrylamido -2- Methyl propane sulfonic acid, 3-acetylaminoaniline are uniformly mixed, and obtain compositions of olefines, then obtain olefin(e) fibre through melt spinning；It will Polytetrafluoroethylparticle particle and five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (triethoxysilicanes Base) -3, melt spinning method is used after the mixing of 3 '-bipyridyls, polytetrafluoroethylene fibre is prepared；By olefin(e) fibre, polytetrafluoro Vinyl fiber is blended by 20: 1 mass ratio progress, obtains toughening layer；
(2) aluminum phosphate and talcum powder, yttrium oxide are sintered 25~35 minutes at 800 DEG C after mixing, are then comminuted into average The powder that partial size is 250 nanometers；It disperses the powder into 30 times of powder weight of ethyl alcohol, the isomery of powder weight 0.5% is added Tridecanol polyoxyethylene ether stirs 85~95 minutes in 50 DEG C, the P-hydroxybenzoic acid first of powder weight 0.5% is then added Ester stirs 25~35 minutes, last drying to obtain filler；4- (2- hydroxyl is added in pentaerythritol tetraacrylate, polyethylene glycol Ethyl) -1- piperazine ethanesulfonic acid half in sodium salt buffer, is added filler and phthalic acid two contracts after stirring 45~55 minutes Water glyceride is added trifluoromethanesulfonic acid lanthanum and butyl acrylate after stirring 65~75 minutes in 80 DEG C, continues stirring 2~3 hours, Obtain adhesives；
(3) adhesives is coated on Kapton surface, 90 DEG C are heated 5~8 minutes, and the polyamides with adhesive layer is obtained Imines film；Adhesives is coated on toughening layer surface, 60 DEG C are heated 10~15 minutes, and the toughening with adhesive layer is obtained Layer；Then the compound Kapton with adhesive layer and the toughening layer for having adhesive layer, it is sub- that hot pressing obtains high tenacity polyamides Amine material；The adhesive layer is between Kapton and toughening layer.
2. high toughness polyimide material according to claim 1, it is characterised in that: in step (1), screw rod melting extrusion adds The extrusion temperature of work is 180~200 DEG C, and screw speed control is 150~175 revs/min, and residence time of the material in screw rod be 2~3 minutes.
3. high toughness polyimide material according to claim 1, it is characterised in that: in step (1), melt spinning obtains alkene Temperature is 190~200 DEG C when hydrocarbon fiber, and spinning speed is 400~600 ms/min；When melt spinning obtains polytetrafluoroethylene fibre Temperature is 310~320 DEG C, and spinning speed is 600~700 ms/min.
4. high toughness polyimide material according to claim 1, it is characterised in that: in step (1), bisphenol A cyanate ester Monomer, triglycidyl group cyamelide ester monomer, nonylphenol polyoxyethylene ether and zinc titanate mass ratio be 1: 0.8: 0.4 :0.02；Polyethylene, polypropylene, methine succinic acid and cyanate performed polymer mass ratio be 1: 1.1: 0.2: 0.3；Alkene grain Son, dimethyl tin oxide, 2- acrylamide-2-methylpro panesulfonic acid, 3-acetylaminoaniline mass ratio be 1: 0.0005: 0.2:0.08；Polytetrafluoroethylparticle particle, five nitric hydrate bismuths, antimony oxide, uramit, acrylamide, 5,5 '-bis- (three Ethyl-silicone) -3,3 '-bipyridyls mass ratio be 1: 0.009: 0.18: 0.2: 0.3: 0.12.
5. high toughness polyimide material according to claim 1, it is characterised in that: in step (2), aluminum phosphate, talcum powder, The mass ratio of yttrium oxide is 5: 1: 0.01；Pentaerythritol tetraacrylate, polyethylene glycol, 4- (2- ethoxy) -1- piperazine Half sodium salt buffer of sulfonic acid, filler, o-phthalic acid diglycidyl ester, trifluoromethanesulfonic acid lanthanum, butyl acrylate mass ratio It is 1: 0.5: 6: 0.2: 0.4: 0.001: 0.6.
6. high toughness polyimide material according to claim 1, it is characterised in that: in step (2), 4- (2- ethoxy)- The mass concentration of half sodium salt buffer of 1- piperazine ethanesulfonic acid is 2%.
7. high toughness polyimide material according to claim 1, it is characterised in that: in step (3), the pressure of the hot pressing For 1.2MPa, temperature is 125 DEG C, and the time is 4~6 minutes.
8. high toughness polyimide material according to claim 1, it is characterised in that: the Kapton with a thickness of 20~100 microns；The toughening layer with a thickness of 8~25 microns.
9. high toughness polyimide material described in claim 1 is preparing the application in polyimides plate.
CN201811131928.8A 2016-08-02 2016-08-02 A kind of high toughness polyimide material and its application Pending CN109439208A (en)

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