CN105504810A - Method for preparing high-intensity and high-modulus polyimide-fiber-reinforced polyimide sheet through continuous forming - Google Patents
Method for preparing high-intensity and high-modulus polyimide-fiber-reinforced polyimide sheet through continuous forming Download PDFInfo
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- CN105504810A CN105504810A CN201610025449.2A CN201610025449A CN105504810A CN 105504810 A CN105504810 A CN 105504810A CN 201610025449 A CN201610025449 A CN 201610025449A CN 105504810 A CN105504810 A CN 105504810A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The invention discloses a method for preparing a high-strength and high-modulus polyimide-fiber-reinforced polyimide sheet through continuous forming. The method includes the following steps of conducting curtain coating or coating on the surface of polyimide fiber cloth through a polyamide acid solution, making gaps of the polyimide fiber cloth sufficiently soaked through repeated roller pressing, sending the polyimide fiber cloth to a solvent volatizing furnace to remove solvent and form a half-dry gel film, conducting partial imidization through an infrared furnace to obtain a lower surface continuous film, conducting secondary curtain coating through polyamide acid, forming a continuous film layer on the upper surface of the fiber cloth, conducting imidization in the universal cyclization process of a polyimide film, cutting edges, and conducting rolling to obtain the high-strength and high-modulus polyimide-fiber-reinforced polyimide sheet. The material prepared through the method has the advantages of fiber of being high in strength and modulus and the advantages of the thin film of being high in toughness, sealing performance and the like at the same time; the upper surface and the lower surface are provided with smooth continuous film layers respectively, and a brand-new polyimide product form is achieved after thin film, fiber and resin molding powder.
Description
Technical field:
The present invention relates to high-performance compound foil material preparing technical field, be specifically related to the continuously shaped technology of preparing that a kind of high-strength high modulus polyimide fiber strengthens polyimide.
Background technology:
Polyimide material is with the fragrant heterocyclic chemistry structure of its uniqueness, there is excellent resistance to elevated temperatures, mechanical property, dielectric properties and the performance such as resistance to uv irradiation and solvent resistant corrosion, have a wide range of applications in fields such as defence and military, aerospace, electron and electricians.The related products of polyimide comprises polyamic acid glue, Kapton, fiber, resin mold molding powder etc.Wherein extensive with the product application of film morphology existence, and the maximum ga(u)ge of film is generally no more than 150 μm, intensity is between 100 ~ 300MPa, and modulus is between 1 ~ 8GPa.But thickness is greater than the Kapton of 150 μm or sheet-like material does not but have the product of mass-producing to occur so far.This is mainly owing to the process complexity that polyimide material is shaping, and preparing sheet-like material can have two kinds of methods, and one is shaping at high temperature under high pressure by resin mold molding powder; Another kind is by polyamic acid curtain coating, desolventize, imidization is shaping.But the former is difficult to realize mass-producing, continuous prodution due to the condition of molding of harshness, latter causes product to shrink modification because solvent and the dehydration of imidization closed loop generate the problems such as small molecules, and cannot obtain desirable product.
Polyimide fiber is a kind of high-performance organic fibre just grown up in recent years, not only has the performance characteristics that polyimide material is all, also has very high strength and modulus, obtains the concern of height in the research of field of compound material.Publication number is describe a kind of polyimide fiber in the patent of 103319890A to strengthen polyimide resin based matrix material and preparation method thereof, PMR method during the method is shaping by means of polyimide resin, by temperature programming desolvation, then the unsaturated link(age) crosslinking curing of High Temperature High Pressure initiation polyimide resin molecular chain-end is shaping, thus obtains the matrix material of full polyimide self-enhancement.Because fibre reinforcement and resin matrix have similar chemical structure, so this matrix material has good boundary strength and resistance to elevated temperatures and mechanical property.But the forming method adopted due to it needs High Temperature High Pressure equally, so compare the compression molding being suitable for the sample with specified shape size, and be not suitable for the large scale continuous prod of sheet material.
Compared with aforesaid method, the present invention adopts polyamic acid as the material of main part of preparation polyimide, by itself and polyimide fiber cloth by soaking, roll-in, desolventize, part imidization, secondary dipping, roll-in, knifing, desolventize, the technique such as imidization realizes the continuous prodution that thickness is greater than the polyimide composite sheet of 150 μm and prepares.Namely first by soaking, roll-in, desolventize, the process of part imidization, control polyamic acid viscosity and impregnation resin content, form the rete of continuous and derivable at fabric lower surface in conjunction with action of gravity, then by secondary dipping, roll-in, knifing, desolventize, the process of imidization forms smooth and continuous rete at fabric upper surface, also can only through soaking, roll-in, desolventize, the operation such as imidization obtains the sheeting that lower surface is smooth, upper surface still retains fiber grain.The advantage of the method has: (1) polyimide fiber specific surface area is large, be conducive to removing the small molecules that solvent in polyamic acid and reaction generate, and well solves the air bubble problem in the film preparation of polyimide super thick; (2) polyimide fiber cloth can be used as skeletal support, solves the dimensional contraction problem in super thick film preparation; (3) polyimide fiber has very high strength and modulus, serve in sheeting mechanical property strengthen effect, make the strength and modulus of this sheeting comparatively film had significant lifting; (4) the method can realize mass-producing, the continuous prodution preparation of polyimide compound foil material.
At present, two-sided smooth, that continuous print polyimide fiber the strengthens polyimide compound foil material method of this preparation described in the invention yet there are no bibliographical information.Technology provided by the present invention, can realize the continuous prodution that polyimide fiber strengthens polyimide compound foil, is very beneficial for technology and the product up-gradation transformation of polyimide fiber and film production enterprise.Be adapted to pass through condensation polymerization and prepare polyamic acid, casting film-forming, then prepared all systems of polyimide by cyclisation, low to base film selectivity, applied widely.What is more important can prepare the sheet-like material exceeding conventional films thickness (150 μm), and this is the product form be badly in need of in current polyimide material.Therefore, Method and Technology provided by the present invention is for the bottleneck problem solved in super thick membrane-film preparation process, and the product category enriching polyimide material has very important realistic meaning.
Summary of the invention:
The object of this invention is to provide a kind of polyimide fiber with high strength and high-modulus and strengthen polyimide compound foil material, this material had both had high strength and high-modulus, the toughness also with thin-film material and the resistance to air loss of fiber, simultaneously because chemical structure is similar, there is good interface bond strength.
Another object of the present invention is to provide a kind of method with the polyimide compound foil material continuous production of high strength and high-modulus, and this method can solve the problem such as bubble and dimensional contraction in current polyimide super thick film or sheeting preparation technology.
Particular content of the present invention and technical scheme as follows:
The continuously shaped method preparing high-strength high modulus polyimide fiber enhancing polyimide, is characterized in that, comprise the following steps:
A: by the polyamic acid solution of synthesis through curtain coating or impregnation in polyimide fiber cloth surface, through roll squeezer, fiber and glue are fully infiltrated, discharge unnecessary glue by pressure-controlling;
B: the latex bonded fibre cloth obtained in steps A is desolventized through the heating of solvent evaporates stove and forms semi-drying gel-film, then through the imidization of infra-red furnace part;
C: carry out secondary curtain coating or impregnation to the part imidization compound foil obtained in step B, makes polyamic acid fully cover cloth surface and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness through roll squeezer;
D: the laminated film obtained by step C is desolventized by solvent evaporates stove and forms semi-drying gel-film, then slice surfaces planeness is improved through roll squeezer, carry out abundant cyclisation through imidization stove again, eventually pass cutting edge, winding process obtain high-strength high modulus polyimide fiber strengthen polyimide.
The raw material of the polyimide fiber cloth selected is high-strength and high-modulus type polyimide fiber, and fibre strength is greater than 1.5GPa, and modulus is greater than 80GPa.
Mainly through the thickness of the area density adjustment thin slice of cloth, cloth area density scope is 20 ~ 500g/m
2.
The polyamic acid solution selected is the polyimide precursor solution that the mixed polycondensation of any type dianhydride or polynary acid anhydride and diamines or polyamine or copolycondensation obtain.
In steps A, the solid content of polyamic acid solution controls between 10wt ~ 20wt%, viscosity controller is between 500cp ~ 2000cp, in polyamic acid, the mass ratio of solids content and polyimide fiber cloth is between 0.2 ~ 1, ensures that polyamic acid and cloth are fully infiltrated.
Adopt gradient increased temperature in step B, control solvent in the once-combined thin slice obtained and be less than 5%, imidization degree is greater than 50%.
In step C, the solid content of polyamic acid solution controls between 10wt% ~ 20wt%, viscosity controller between 2000cp ~ 20000cp, control polyimide fiber cloth account for massfraction after compound foil solidification 30% ~ 70% between.
Step D first desolventizes through solvent evaporates stove and obtains semi-drying gel compound foil, solvent controls at 10wt% ~ 25wt%, adopt roll squeezer to obtain the smooth gel compound foil of any surface finish again, then through the abundant imidization of imidization stove, each section of heating all adopts the mode of gradient increased temperature.
The latex bonded fibre cloth that also steps A can be obtained directly desolventizes through solvent evaporates stove and forms semi-drying gel-film, then slice surfaces planeness is improved through roll squeezer, carry out abundant cyclisation through imidization stove again, eventually pass cutting edge, winding process obtain high-strength high modulus polyimide fiber strengthen polyimide.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts the mode of twice impregnation, can obtain upper and lower surface all smooth, polyimide sheet material containing polyimide fiber skeleton.
2. the reinforcement that compound foil material provided by the invention adopts is polyimide fiber, sheet base is Kapton, all be made up of polyimide material, interface bond strength is high, played fiber and film performance characteristics separately to the full extent, material has excellent mechanical property, resistance to elevated temperatures, dimensional stability, electrical insulating property, resistance to air loss and wave.
3. the present invention can the continuous production thickness polyimide sheet material that is greater than 150 μm, enrich the kind of polyimide, fully can meet the application demand for high temperature resistant, high strength, high heat insulating lamella material in current structure material or electromagnetic wave transparent material, good market prospects.
Accompanying drawing illustrates:
Fig. 1: the continuously shaped technological line schematic diagram preparing high-strength high modulus polyimide fiber enhancing polyimide of the present invention;
Fig. 2: the high-strength high modulus polyimide fiber prepared by the present invention strengthens the digital photograph of polyimide sheet material.
Embodiment:
Below in conjunction with specific embodiment, set forth invention further.
Embodiment 1
A: by the PMDA-ODA system polyamic acid solution (viscosity 1500cp) of solid content 12%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 180g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.5;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be the PMDA-ODA system polyamic acid solution (viscosity 10000cp) of 15% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 50% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 150 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 2
A: by the BPDA-ODA system polyamic acid solution (viscosity 800cp) of solid content 15%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 120g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.3;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be the BPDA-ODA system polyamic acid solution (viscosity 12000cp) of 18% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 60% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 300 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 3
A: by the BPDA-PDA system polyamic acid solution (viscosity 1400cp) of solid content 15%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 150g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.5;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be the BPDA-PDA system polyamic acid solution (viscosity 16000cp) of 15% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 60% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 150 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 4
A: by the 6FDA-ODA system polyamic acid solution (viscosity 600cp) of solid content 10%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 100g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.5;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be the 6FDA-ODA system polyamic acid solution (viscosity 5000cp) of 15% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 55% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 300 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 5
A: by BPDA-ODA-PDA copolycondensation system polyamic acid solution (viscosity 1500cp) of solid content 10%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 70g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.4;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be BPDA-ODA-PDA copolycondensation system polyamic acid solution (viscosity 5000cp) of 15% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 62% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 150 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 6
A: by BPDA-ODA-PDA copolycondensation system polyamic acid solution (viscosity 1500cp) of solid content 10%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 300g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 1;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be BPDA-ODA-PDA copolycondensation system polyamic acid solution (viscosity 5000cp) of 15% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 40% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 150 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 7
A: by the BTDA-ODA polyamic acid solution (viscosity 1500cp) of solid content 12%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 80g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.5;
B: latex bonded fibre cloth steps A obtained, through solvent evaporates stove, desolventizes, then carries out part imidization through the gradient-heated stove of 200 DEG C ~ 300 DEG C in the gradient scope of 80 DEG C ~ 150 DEG C;
C: be the BTDA-ODA polyamic acid solution (viscosity 18000cp) of 16% by solid content, be cast to the part imidization slice surfaces that step B obtains, make the abundant cover sheet surface of polyamic acid by pressure roller and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness, polyimide fiber cloth is made to account for 50% of the rear massfraction of compound foil solidification;
D: the compound foil obtained by step C is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 150 DEG C desolventizes and forms semi-drying gel-film, solvent is between 10wt% ~ 25wt%, then slice surfaces planeness is improved through pressure roller, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 8
A: by the ODPA-ODA polyamic acid solution (viscosity 800cp) of solid content 14%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 260g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.66;
B: latex bonded fibre cloth steps A obtained is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 300 DEG C desolventizes and forms semi-drying gel-film, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
Embodiment 9
A: by the PMDA-ODA polyamic acid solution (viscosity 1500cp) of solid content 15%, curtain coating is at high-strength and high-modulus type polyimide fiber cloth (area density 410g/m
2) surface, and prolong steel band and travel through pressure roller, cloth and polyamic acid solution are fully infiltrated, discharges unnecessary glue, in control polyamic acid, the mass ratio of solid and polyimide fiber cloth is 0.66;
B: latex bonded fibre cloth steps A obtained is by solvent evaporates stove, the gradient scope of 80 DEG C ~ 230 DEG C desolventizes and forms semi-drying gel-film, again through the abundant cyclisation in the gradient scope of 300 DEG C ~ 500 DEG C of imidization stove, eventually pass the operation such as cutting edge, rolling and obtain high-strength high modulus polyimide fiber enhancing polyimide compound foil material.
The test result of each embodiment of table 1
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets reference the above embodiments are to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
1. the continuously shaped method preparing high-strength high modulus polyimide fiber enhancing polyimide, is characterized in that, comprise the following steps:
A: by the polyamic acid solution of synthesis through curtain coating or impregnation in polyimide fiber cloth surface, through roll squeezer, fiber and glue are fully infiltrated, discharge unnecessary glue by pressure-controlling;
B: the latex bonded fibre cloth obtained in steps A is desolventized through the heating of solvent evaporates stove and forms semi-drying gel-film, then through the imidization of infra-red furnace part;
C: carry out secondary curtain coating or impregnation to the part imidization compound foil obtained in step B, makes polyamic acid fully cover cloth surface and form the rete covered continuously, by accurate scraper controlling diaphragm layer thickness through roll squeezer;
D: the laminated film obtained by step C is desolventized by solvent evaporates stove and forms semi-drying gel-film, then slice surfaces planeness is improved through roll squeezer, carry out abundant cyclisation through imidization stove again, eventually pass cutting edge, winding process obtain high-strength high modulus polyimide fiber strengthen polyimide.
2. preparation method as claimed in claim 1, it is characterized in that, the raw material of the polyimide fiber cloth selected is high-strength and high-modulus type polyimide fiber, and fibre strength is greater than 1.5GPa, and modulus is greater than 80GPa.
3. preparation method as claimed in claim 1, is characterized in that, mainly through the thickness of the area density adjustment thin slice of cloth, cloth area density scope is 20 ~ 500g/m
2.
4. preparation method as claimed in claim 1, is characterized in that, the polyamic acid solution selected is the polyimide precursor solution that the mixed polycondensation of any type dianhydride or polynary acid anhydride and diamines or polyamine or copolycondensation obtain.
5. preparation method as claimed in claim 1, it is characterized in that, in steps A, the solid content of polyamic acid solution controls between 10wt ~ 20wt%, and viscosity controller is between 500cp ~ 2000cp, and in polyamic acid, the mass ratio of solids content and polyimide fiber cloth is between 0.2 ~ 1.
6. preparation method as claimed in claim 1, is characterized in that, adopt gradient increased temperature in step B, and control solvent in the once-combined thin slice obtained and be less than 5%, imidization degree is greater than 50%.
7. preparation method as claimed in claim 1, it is characterized in that, in step C, the solid content of polyamic acid solution controls between 10wt% ~ 20wt%, viscosity controller between 2000cp ~ 20000cp, control polyimide fiber cloth account for massfraction after compound foil solidification 30% ~ 70% between.
8. preparation method as claimed in claim 1, it is characterized in that, step D first desolventizes through solvent evaporates stove and obtains semi-drying gel compound foil, solvent controls at 10wt% ~ 25wt%, roll squeezer is adopted to obtain the smooth gel compound foil of any surface finish again, then through the abundant imidization of imidization stove, each section of heating all adopts the mode of gradient increased temperature.
9. preparation method as claimed in claim 1, it is characterized in that, the latex bonded fibre cloth that also steps A can be obtained directly desolventizes through solvent evaporates stove and forms semi-drying gel-film, then slice surfaces planeness is improved through roll squeezer, carry out abundant cyclisation through imidization stove again, eventually pass cutting edge, winding process obtain high-strength high modulus polyimide fiber strengthen polyimide.
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| CN201610025449.2A CN105504810A (en) | 2016-01-07 | 2016-01-07 | Method for preparing high-intensity and high-modulus polyimide-fiber-reinforced polyimide sheet through continuous forming |
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| CN201610025449.2A CN105504810A (en) | 2016-01-07 | 2016-01-07 | Method for preparing high-intensity and high-modulus polyimide-fiber-reinforced polyimide sheet through continuous forming |
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| CN105504810A true CN105504810A (en) | 2016-04-20 |
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