CN103483611B

CN103483611B - Preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method

Info

Publication number: CN103483611B
Application number: CN201310473064.9A
Authority: CN
Inventors: 田佳乐
Original assignee: SUZHOU KELAIMEI HIGH POLYMER MATERIAL SCIENCE & TECHNOLOGY Co Ltd
Current assignee: Wuhan Sulong Decoration Engineering Co ltd
Priority date: 2013-10-11
Filing date: 2013-10-11
Publication date: 2015-08-12
Anticipated expiration: 2033-10-11
Also published as: CN103483611A

Abstract

The invention discloses a kind of preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method, adopt polyacrylonitrile base material as raw material, preoxidised polyacrylonitrile film is obtained after described polyacrylonitrile base material is carried out pre-oxidation in a heated condition, described Heating temperature is less than the fusing point of described polyacrylonitrile base material, and be greater than the heat decomposition temperature of polyacrylonitrile base material, the heatproof temperature of described preoxidised polyacrylonitrile film is 200-500 DEG C, wherein, the thickness of described polyacrylonitrile base material is 0.025-3mm, and the fusing point of described polyacrylonitrile base material is greater than its heat decomposition temperature, the present invention adopts polyacrylonitrile as raw material, because the cost of polyacrylonitrile raw material is low, is thus greatly beneficial to the manufacture optimization in application industry field and falls this.

Description

Preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method

Technical field

The present invention relates to processing film utilisation technology, be specifically related to a kind of preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method.

Background technology

Polyacrylonitrile (polyacrylonitrile, PAN) in polymer side chain owing to there is the very strong cyano group (-CN) of polarity, can produce strong interaction force between cyano group causes the fusing point of PAN (theoretical value is 319 DEG C) higher than its heat decomposition temperature (being about 250 DEG C), be difficult to adopt melting method to process, therefore, in prior art, the general solvent spinning working method that adopts prepares PAN fiber, its concrete evolution is: nineteen forty-one, Dupont (Du Pont) company develops dimethyl formamide (DMF) and carries out dry-spinning as the solvent of PAN, within 1958, american cyanamide (American Cyanamid) company is using sodium thiocyanate water solution as solvent, develop the wet spinning technology of PAN, be solvent spinning working method.

But, in the spinning solution of existing solvent spinning working method, a large amount of solvent is needed to dissolve PAN raw material completely, solvent generally need account for the 75-90wt% in spinning solution, even higher than more than 90wt%, and these solvents are generally corrosive inorganic solvent or volatile organic solvent, as dimethyl sulfoxide (DMSO) (DMSO), N,N-DIMETHYLACETAMIDE (DMAc), nitric acid, α-pyridine alkane ketone, tetramethylene sulfone etc., and finally only have the spinning solution of 10-25wt% in converted products, wherein, the recovery of solvent and purification, and waste gas or wastewater treatment not only need to drop into high energy consumption and processing units investment, bring very large potential safety hazard to especially environment and production simultaneously.In addition, solvent spinning working method also can only prepare PAN fiber, and cannot prepare PAN film.

For this reason, people are exploring the fusing point reducing PAN always, and then make, by melting method processing preparation PAN fiber or PAN film, there is feasibility, the main mode adopted is elasticizer plasticizing method and chemical copolymerization plasticization process at present, wherein, chemical copolymerization plasticization process prepares PAN by melt-processed, specifically introduce second comonomer or Third monomer in the course of the polymerization process, reduce the fusing point of PAN polymkeric substance, but this method often reduces mechanical property and the thermal characteristics of PAN polymkeric substance, and range of application is extremely restricted; And elasticizer plasticizing method refers to and adds softening agent in the pan, in prior art, the softening agent of PAN is mainly water, is the vaporization at processing temperatures of anti-sealing, usually adopts pressurization to melt the shaping method that then reduces pressure, and technological process is difficult to control.

Lower mask body introduces some prior aries about the polyacrylonitrile polymer of melt-processable:

Publication number is that the Chinese patent of CN100999604A discloses a kind of soluble polyacrylic cyanide composite and preparation method thereof; the softening agent contained in mixture is ionic liquid; its preparation method be by mass percent be 72 ~ 98% polyacrylonitrile and mass percent be 2 ~ 28% ionic liquid mixes; stir at 25 ~ 90 DEG C; prepared mixture can melting at 120 ~ 155 DEG C; polyacrylonitrile mixture can be used as the raw material of polyacrylonitrile fibre, film etc.; ionic liquid kind is many; nontoxic; non-volatility, is used in environment protection.

And for example publication number is that the Chinese patent of CN101323656A discloses a kind of acrylonitrile copolymer and its production and use, vinyl cyanide on this acrylonitrile copolymer molecular chain and the mol ratio of second comonomer unit are 2: 1 ~ 19: 1, and filling a prescription is: acrylonitrile monemer 70.0 ~ 90.0MOL%; Second comonomer 10.0 ~ 30.0MOL%; Initiator and chain tra nsfer control agent account for 0.1 ~ 16.2MOL% and the 0.05 ~ 5.0MOL% of monomer total amount respectively.This preparation method adopts acrylonitrile compolymer composition formula of the present invention and following technique: in reaction vessel, add appropriate deionized water, nitrogen wash 5 ~ 400 minutes, temperature 0 ~ 70 DEG C; Then disposablely described chain tra nsfer control agent and initiator is added; Add acrylonitrile monemer and second comonomer in the mixing container, fully after mixing, slowly drop in described reaction vessel, dropwise rear continuation stirring 20 ~ 40 minutes, filtration product, deionized water wash three times, after vacuum-drying and get final product.

For another example publication number is the preparation method that the Chinese patent of CN102806022A discloses a kind of polyacrylonitrile-radical microporous membrane, and the method adopts TIPS technique, comprising: 1. prepare melting acrylonitrile copolymer; Employing molar ratio is acrylonitrile monemer and the second comonomer mixture of 95/5 ~ 70/30, prepares melting acrylonitrile copolymer through polymerization technique; 2. prepare acrylonitrile group film-casting liquid; Gained multipolymer and thinner are added in stirring tank by 1/9 ~ 5/5wt% weight ratio, is heated to 140 ~ 230 DEG C, deaeration 10 ~ 60min after formation homogeneous solution, obtained PAN base film-casting liquid; 3. prepare microporous membrane; Preparation flat sheet membrane method is poured into by described film-casting liquid to be preheated to calendaring molding in 150 ~ 230 DEG C of moulds, after cooling, solidification, extraction and get final product; Preparing hollow membrane method is pour in spinning-drawing machine by described film-casting liquid, extrudes at 150 ~ 230 DEG C, through extraction thinner after and get final product.

But, these patents are by reducing the fusing point of polyacrylonitrile mixture as the softening agent of polyacrylonitrile mixture or employing acrylonitrile copolymer respectively by ionic liquid, and then realizing polyacrylonitrile mixture, can to carry out melt-processed under lower than the condition of its heat decomposition temperature shaping, but these fusing points preparing shaping polyacrylonitrile film are lower than its heat decomposition temperature, in practice, needing the polyacrylonitrile film shaping to these to carry out, following process is modified could realize the application of final industry, therefore the heat decomposition temperature that the temperature condition of these following process modifications must be greater than polyacrylonitrile film could realize processing modified, and the fusing point of the polyacrylonitrile film prepared by these patents above-mentioned is lower than its heat decomposition temperature, when can cause also not arriving processing modified required temperature condition, polyacrylonitrile film melts, and then cause realizing processing modified, polyacrylonitrile film is finally caused to carry out industry application.

Simultaneously due to the protective material of the good characteristics such as having as needed of current each application industry use is fire-retardant, heatproof, resistance to chemical attack, as the protective clothing material of firefighter, need the effectively insulating graphite film with superior insulative properties, and need the conductive graphite film etc. in regular stratiform with superior conductive characteristic, all there is preparation cost higher, there is for preparation the conductive graphite film in regular stratiform of superior conductive characteristic, due to technical limitation, prior art mainly adopts Kapton as raw materials, successively through carburizing reagent, the conductive graphite film in regular stratiform with superior conductive characteristic is finally prepared after greying reaction, because the use cost of Kapton is high, its price is about per kilogram 2000 Renminbi, can only use on high-end electric equipment products at present, because cost factor greatly constrains the range of application of this product.

In conjunction with mentioned above, cheap due to polyacrylonitrile material, use cost is low, its cost is almost about 1/10th of Kapton, if seek to obtain a kind of polyacrylonitrile film realizing following process modification, and after making improvements art breading, replace the material of some preparation cost costlinesses that current each application industry uses, simultaneously owing to there is not cost factor, electric equipment products and other industries of other low and middle-ends can be applied to especially, effectively expand application industry scope, this all has height meaning for whole industry or even several industries.

Therefore, comprehensive foregoing, needs a kind of technical scheme of urgent searching to solve above-mentioned technical problem.

Summary of the invention

In view of this, the object of the present invention is to provide a kind of preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method, preparation cost is low, is thus greatly beneficial to the manufacture optimization in application industry field and falls this.

Present inventor is after the technical problem that conscientiously have studied background technology existence, find, really to realize polyacrylonitrile film and can carry out the final industry application of the modified realization of following process, first need the fusing point of the polyacrylonitrile film guaranteeing to prepare higher than its heat decomposition temperature, otherwise, before polyacrylonitrile does not reach thermolysis modification temperature, polyacrylonitrile just melts, thus cause cannot completing processing modified at all, but the disclosed mode can carrying out melt-processed to polyacrylonitrile raw material at present, mostly reduced the fusing point of polyacrylonitrile raw material as the softening agent of polyacrylonitrile raw material or employing acrylonitrile copolymer by ionic liquid, and then realizing polyacrylonitrile raw material, can to carry out melt-processed under lower than the condition of its heat decomposition temperature shaping, but cause these fusing points preparing shaping polyacrylonitrile film again can lower than its heat decomposition temperature, as needed, publication number polyacrylonitrile film disclosed in the Chinese patent of CN101323656A is carried out the modified realization of following process final industry application time, the plasma softening agent contained in this polyacrylonitrile film must be removed by complicated procedures of forming such as extractions, just can guarantee that the fusing point of polyacrylonitrile film is higher than its heat decomposition temperature, practical application high cost, and the polyacrylonitrile film adopting acrylonitrile copolymer to prepare cannot make it can carry out following process modification by operation process especially at all, to realize final industry application.

And as described in background technology, elasticizer plasticizing method refers to adds large water gaging (accounting for 40wt% or more than the 40wt% of total raw material system) in polyacrylonitrile raw material, water is as the softening agent of PAN, reduce on polyacrylonitrile polymer side chain and can produce strong interaction force between cyano group, thus reduce the fusing point of material system, for the vaporization at processing temperatures of anti-sealing, usually adopt pressurization to melt the shaping method that then reduces pressure, technological process is difficult to control; And, in the process of cooling melt extruding technique, owing to containing large water gaging in melt, because water volatilization can cause finally preparing in the shaping polyacrylonitrile film obtained to there is a large amount of bubbles, affect the Forming Quality of polyacrylonitrile film.

Based on present inventor based on the development Experience for many years to polyacrylonitrile material and melting coextrusion process, and through great many of experiments, polyacrylonitrile material is proposed to dissolve in a solvent, and the mass parts of solvent is too much unsuitable, otherwise as the spinning solution used in existing solvent spinning working method, its solvent accounts for the 75-90wt% in spinning solution, even higher than more than 90wt%, viscosity is too low, minimum melt strength required in melting coextrusion process cannot be reached at all, thus cannot prepare and be applicable to carrying out following process, thickness is the polyacrylonitrile film of 0.025-3mm, the present invention, under the prerequisite guaranteeing melt strength needed for melting coextrusion process, by being dissolved in a solvent by polyacrylonitrile material, significantly can reduce the melt temperature of material system.

The applicant contriver also through in a large number investigation and analytical work after, discovery is cheap due to polyacrylonitrile material, use cost is low, its cost is almost about 1/10th of Kapton, if seek to obtain a kind of polyacrylonitrile base material (polyacrylonitrile film as high in density) realizing following process modification, and after making improvements art breading, replace the material of some cost intensive that current each application industry uses, simultaneously owing to there is not cost factor, electric equipment products and other industries of other low and middle-ends can be applied to especially, effectively expand application industry scope, this all has height meaning for whole industry or even several industries.Hereafter will specifically introduce concrete technical scheme of the present invention.

To achieve these goals, technical scheme provided by the invention is as follows:

A kind of preparation method of preoxidised polyacrylonitrile film, adopt polyacrylonitrile base material as raw material, preoxidised polyacrylonitrile film is obtained after described polyacrylonitrile base material is carried out pre-oxidation in a heated condition, described Heating temperature is less than the fusing point of described polyacrylonitrile base material and is greater than the heat decomposition temperature of polyacrylonitrile base material, the heatproof temperature of described preoxidised polyacrylonitrile film is 200-500 DEG C, wherein, the thickness of described polyacrylonitrile base material is 0.025-3mm, and the fusing point of described polyacrylonitrile base material is greater than its heat decomposition temperature.

Preferably, described polyacrylonitrile base material is polyacrylonitrile film, and the preparation method of described polyacrylonitrile film comprises following operation steps:

A), by the polyacrylonitrile of 60-90wt% and the auxiliary agent of 10-40wt% blended, obtain material system, the melt temperature of described material system is less than the heat decomposition temperature of described polyacrylonitrile;

B), the material system that above-mentioned steps a) obtains is carried out melt extruding art breading, describedly melt extrude technique and comprise heating, extrusion moulding and cooling step successively, described Heating temperature is more than or equal to the melt temperature of described material system and is less than the heat decomposition temperature of described polyacrylonitrile;

C), obtain polyacrylonitrile film, the thickness of described polyacrylonitrile film is 0.025-3mm;

Wherein, described auxiliary agent comprises the solvent of 60-100wt%, and described solvent is selected from any one or a few the mixing in dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, dimethyl formamide, Sodium Thiocyanate 99, nitric acid, α-pyridine alkane ketone, tetramethylene sulfone, zinc chloride.

Preferably, described auxiliary agent comprises the thickening material of 1-30wt%, and described thickening material is selected from any one or a few mixing of polyoxyethylene glycol, polyvinyl alcohol, hydroxylated cellulose, polyacrylamide, for improving the melt strength of material system;

Described auxiliary agent comprises the water of 1-30wt%, dissolves each other with described thickening material.

Preferably, after described step b) completes, before step c) carries out, also comprise:

C0), two-way stretch process is carried out to the polyacrylonitrile film that described step b) obtains.

Preferably, described step b) specifically comprises:

B10), the material system that above-mentioned steps a) obtains is joined in singe screw or twin screw extruder;

B20), to described material system carry out screw rod shearing and heat effect, described Heating temperature is more than or equal to the melt temperature of described material system, and is less than the heat decomposition temperature of described polyacrylonitrile, and described material system forms molten mass;

B30), by above-mentioned steps b20) molten mass extrusion moulding to the thickness that formed is the melting thin slice of 0.025-3mm;

B40), by above-mentioned steps b30) the melting thin slice curtain coating to refrigerating unit that obtains cools, and in process of cooling, the auxiliary agent of 80-100% is volatilized;

B50), cooled form film is passed through pull roll assembly rolling.

Preferably, described refrigerating unit/and described pull roll assembly are placed in enclosed space, and described enclosed space is marked with steam, and the composition of described steam comprises auxiliary agent.

Preferably, described polyacrylonitrile base material is polyacrylonitrile fibre cloth, and described polyacrylonitrile fibre cloth adopts polyacrylonitrile protofibril cloth through coating or infiltrates polyacrylonitrile solution and obtain after drying.

Preferably, a kind of preoxidised polyacrylonitrile film, wherein, described preoxidised polyacrylonitrile film adopts the preparation method of preoxidised polyacrylonitrile film as above to prepare.

Preferably, a kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film as above, wherein, the end temp in described first stage formula intensification is 1600-2000 DEG C; The thermal conductivity of described heat insulation graphite film is equal to or less than 20W/mk.

Preferably, a kind of heat insulation graphite film, wherein, described heat insulation graphite film adopts the preparation method of heat insulation graphite film as above to prepare.

Preferably, a kind of preparation method of conductive graphite film, wherein, is carried out greying under the heating condition that heat insulation graphite film as above in random stratiform is heated up at second-order segmentation and be obtained by reacting conductive graphite film in regular stratiform, wherein, the end temp in described second-order segmentation intensification is 3000-3500 DEG C; The plane thermal conductivity of described conductive graphite film is 1000-1600W/mk.

Preferably, a kind of conductive graphite film, wherein, described conductive graphite film adopts the preparation method of conductive graphite film as above to prepare.

Based on present inventor based on the development Experience for many years to polyacrylonitrile material and melting coextrusion process, and through great many of experiments, the present invention proposes by all or part of for polyacrylonitrile material dissolving in a solvent, the solvent quality part simultaneously controlling to add is with under the prerequisite guaranteeing melt strength needed for melting coextrusion process, significantly can reduce the melt temperature of material system, and then the process of melting coextrusion process can be carried out to material system, prepare polyacrylonitrile film, simultaneously, in the process of cooling of melting coextrusion process, most of solvent can volatilize, therefore can guarantee again that the fusing point of the polyacrylonitrile film finally prepared is higher than its decomposition temperature, guarantee that polyacrylonitrile film can carry out the final industry application of the modified realization of following process, and preparation technology of the present invention is simple, convenient operation and materials'use cost low.

The present invention further optimally, adds thickening material improves material system further viscosity as auxiliary agent in material system, and then improves it and carrying out the melt strength in melting coextrusion process, and in material system, add the water that dissolves each other with thickening material as auxiliary agent, not only can improve the performance that thickening material improves material system viscosity further, also because water can decrease interaction force in polyacrylonitrile between cyano group as softening agent, thus also can further improve polyacrylonitrile solubleness in a solvent, and then meet under the condition of the solvent adding limited mass parts, improve material system and carry out the melt strength in melting coextrusion process, simultaneously, it is the acrylonitrile monemer adopting 90-100wt% that the present invention also proposes polyacrylonitrile, the polymkeric substance that the second comonomer of 0-10wt% and the Third monomer of 0-5wt% prepare after polyreaction, when polyacrylonitrile is comprise the copolymerized polymer that acrylonitrile monemer and second comonomer/and Third monomer prepare after polyreaction, molecule segment due to Co-polypropylene nitrile introduces second comonomer/and Third monomer, decrease the interaction force in polyacrylonitrile between cyano group, thus also can further improve polyacrylonitrile solubleness in a solvent, and then meet under the condition of the solvent adding limited mass parts, improve material system and carry out the melt strength in melting coextrusion process, in above-mentioned Basis of Optimal Technique, the present invention and then can the interpolation mass parts of solvent be controlled in less scope, thus guarantee that material system is melt extruding the melt strength in technological process, guarantee that material system can carry out melt extruding art breading further, finally obtain the polyacrylonitrile film being applicable to carrying out following process, thickness is 0.025-3mm.

The present invention also proposes applicablely to carry out following process by what obtain, thickness is the polyacrylonitrile base material (specifically can comprise polyacrylonitrile film and polyacrylonitrile fibre cloth) of 0.025-3mm, after the processing modified process of different operation, the various product with different high-performance can be prepared, specifically comprise preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film etc., and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, this belongs to the very marvelous technical progress of the industry, truly achieve polyacrylonitrile except except the application of textile fibres field, also can prepare the polyacrylonitrile film and polyacrylonitrile fibre cloth with excellent machinability, and then be applied to different industrial fields.

Accompanying drawing explanation

In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.

Accompanying drawing 1 is the preparation process block diagram of polyacrylonitrile film under the specific embodiment of the invention;

Accompanying drawing 2 is pre-oxidation formula of polyacrylonitrile film under the specific embodiment of the invention.

Embodiment

The embodiment of the invention discloses a kind of preparation method of preoxidised polyacrylonitrile film, adopt polyacrylonitrile base material as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile base material is carried out pre-oxidation in a heated condition, Heating temperature is less than the fusing point of polyacrylonitrile base material and is greater than the heat decomposition temperature of polyacrylonitrile base material, the heatproof temperature of preoxidised polyacrylonitrile film is 200-500 DEG C, wherein, the thickness of polyacrylonitrile base material is 0.025-3mm, and the fusing point of polyacrylonitrile base material is greater than its heat decomposition temperature.

The embodiment of the invention also discloses a kind of preoxidised polyacrylonitrile film, wherein, preoxidised polyacrylonitrile film adopts the preparation method of preoxidised polyacrylonitrile film as above to prepare.

The embodiment of the invention also discloses a kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film as above, wherein, the end temp in first stage formula intensification is 1600-2000 DEG C; The thermal conductivity of heat insulation graphite film is equal to or less than 20W/mk.

The embodiment of the invention also discloses a kind of heat insulation graphite film, wherein, heat insulation graphite film adopts the preparation method of heat insulation graphite film as above to prepare.

The embodiment of the invention also discloses a kind of preparation method of conductive graphite film, wherein, is carried out greying under the heating condition that heat insulation graphite film as above in random stratiform is heated up at second-order segmentation and be obtained by reacting conductive graphite film in regular stratiform, wherein, the end temp in the intensification of second-order segmentation is 3000-3500 DEG C; The plane thermal conductivity of conductive graphite film is 1000-1600W/mk.

The embodiment of the invention also discloses a kind of conductive graphite film, conductive graphite film adopts the preparation method of conductive graphite film as above to prepare.

Based on present inventor based on the development Experience for many years to polyacrylonitrile material and melting coextrusion process, and through great many of experiments, the embodiment of the present invention proposes by all or part of for polyacrylonitrile material dissolving in a solvent, the solvent quality part simultaneously controlling to add is with under the prerequisite guaranteeing melt strength needed for melting coextrusion process, significantly can reduce the melt temperature of material system, and then the process of melting coextrusion process can be carried out to material system, prepare polyacrylonitrile film, simultaneously, in the process of cooling of melting coextrusion process, most of solvent can volatilize, therefore can guarantee again that the fusing point of the polyacrylonitrile film finally prepared is higher than its decomposition temperature, guarantee that polyacrylonitrile film can carry out the final industry application of the modified realization of following process, and the preparation technology of the embodiment of the present invention is simple, convenient operation and materials'use cost low.

The embodiment of the present invention further optimally, adds thickening material improves material system further viscosity as auxiliary agent in material system, and then improves it and carrying out the melt strength in melting coextrusion process, and in material system, add the water that dissolves each other with thickening material as auxiliary agent, not only can improve the performance that thickening material improves material system viscosity further, also because water can decrease interaction force in polyacrylonitrile between cyano group as softening agent, thus also can further improve polyacrylonitrile solubleness in a solvent, and then meet under the condition of the solvent adding limited mass parts, improve material system and carry out the melt strength in melting coextrusion process, simultaneously, it is the acrylonitrile monemer adopting 90-100wt% that the embodiment of the present invention also proposes polyacrylonitrile, the polymkeric substance that the second comonomer of 0-10wt% and the Third monomer of 0-5wt% prepare after polyreaction, when polyacrylonitrile is comprise the copolymerized polymer that acrylonitrile monemer and second comonomer/and Third monomer prepare after polyreaction, molecule segment due to Co-polypropylene nitrile introduces second comonomer/and Third monomer, decrease the interaction force in polyacrylonitrile between cyano group, thus also can further improve polyacrylonitrile solubleness in a solvent, and then meet under the condition of the solvent adding limited mass parts, improve material system and carry out the melt strength in melting coextrusion process, in above-mentioned Basis of Optimal Technique, the embodiment of the present invention and then can the interpolation mass parts of solvent be controlled in less scope, thus guarantee that material system is melt extruding the melt strength in technological process, guarantee that material system can carry out melt extruding art breading further, finally obtain the polyacrylonitrile film being applicable to carrying out following process, thickness is 0.025-3mm.

The embodiment of the present invention also proposes applicablely to carry out following process by what obtain, thickness is the polyacrylonitrile base material (specifically can comprise polyacrylonitrile film and polyacrylonitrile fibre cloth) of 0.025-3mm, after the processing modified process of different operation, the various product with different high-performance can be prepared, specifically comprise preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film etc., and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, this belongs to the very marvelous technical progress of the industry, truly achieve polyacrylonitrile except except the application of textile fibres field, also can prepare the polyacrylonitrile film and polyacrylonitrile fibre cloth with excellent machinability, and then be applied to different industrial fields.

Technical scheme in the present invention is understood better in order to make those skilled in the art person, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, should belong to the scope of protection of the invention.

Embodiment 1:

Shown in Figure 1, a kind of preparation method of polyacrylonitrile film, its operation steps comprises:

A), by the polyacrylonitrile of 80wt% and the auxiliary agent of 20wt% blended, wherein, the copolymerized polymer that polyacrylonitrile is the employing acrylonitrile monemer of 95wt%, the second comonomer of 5wt% prepares after polyreaction, second comonomer be selected from methyl acrylate, methyl methacrylate, methacrylonitrile, vinyl acetate or acrylamide any one, particularly, in the present embodiment, second comonomer is methyl acrylate, and auxiliary agent comprises the water of the solvent of 80wt%, the thickening material of 10wt% and 10wt%; Solvent is selected from any one or a few the mixing in dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, dimethyl formamide, Sodium Thiocyanate 99, nitric acid, α-pyridine alkane ketone, tetramethylene sulfone, zinc chloride, and particularly, in the present embodiment, solvent is N,N-DIMETHYLACETAMIDE; Thickening material is selected from any one or a few mixing of polyoxyethylene glycol, polyvinyl alcohol, hydroxylated cellulose, polyacrylamide, and particularly, in the present embodiment, thickening material is polyoxyethylene glycol; Detect through differential scanning calorimeter, the melt temperature of material system is 220 DEG C;

B), the material system that above-mentioned steps a) obtains is carried out melt extruding art breading, melt extrude technique and comprise heating, extrusion moulding and cooling step successively, Heating temperature is more than or equal to the melt temperature of material system, and is less than the heat decomposition temperature of polyacrylonitrile; In process of cooling, the auxiliary agent of 90% is volatilized, and preferably, step b) specifically comprises in the present embodiment:

B20), screw rod shearing and heat effect are carried out to material system, Heating temperature is more than or equal to the melt temperature of material system, and be less than the heat decomposition temperature of polyacrylonitrile, material system forms molten mass, particularly, in the present embodiment, adopt stage intensification type of heating, particularly, in the present embodiment, each stage Heating temperature is 120 DEG C, 160 DEG C, 200 DEG C, 230 DEG C;

B30), by above-mentioned steps b20) molten mass extrusion moulding to the thickness that formed is 1mm, width is 500mm melting thin slice, natch, in other embodiments, can by the melting thin slice regulating procession parameters to extrude other thickness, preferably, the thickness of melting thin slice is 0.025-3mm, width is 200-1600mm, and these routines being those skilled in the art are selected;

B40), by above-mentioned steps b30) the melting thin slice curtain coating to refrigerating unit that obtains cools, particularly, refrigerating unit is cooling roller, preferably, in the present embodiment, in order to improve cooling performance further, increase by one group of guide roller be connected with cooling roller, driving travelling belt (generally adopting metal drive belt) by guide roller, is also the process of cooling to form film while of transmitting the process of form film.

B50), cooled form film is passed through pull roll assembly rolling, wherein, traction Kun assembly comprises the front haulage roller and rear haulage roller that mutually transmit and connect, the speed of rear haulage roller is greater than the speed of front haulage roller, form film is made to produce molecular orientation along rolling direction, for improving the intensity of form film on rolling direction.

Further preferably, a large amount of bubbles is there is for avoiding the polyacrylonitrile film causing because auxiliary agent volatilizees rapidly in process of cooling finally preparing, affect quality product, preferably, in the present embodiment, refrigerating unit and pull roll assembly are placed in enclosed space, enclosed space is marked with steam, the composition of steam comprises N,N-DIMETHYLACETAMIDE and water, the auxiliary agent of 90% is slowly volatilized, natch, in other embodiments, the volatile quantity that can control auxiliary agent by adjusting concrete process of cooling makes auxiliary agent slowly volatilize, preferably, the auxiliary agent of 80-100% is volatilized,

Detected by melt flow rate (MFR) determinator and obtain melt flow rate (MFR), then calculate melt strength by detecting the melt flow rate (MFR) obtained by calculation formula, after testing, the melt strength of the material system in present embodiment is 1.42 × 10 ⁵pa.s.

Be very known conventional techniques means and common practise owing to melt extruding technique, therefore the present embodiment no longer carries out concrete expansion to operation steps more specifically and repeats.

C0), two-way stretch process is carried out to the polyacrylonitrile film that step b) obtains, the thickness of the polyacrylonitrile film that final molding is obtained is more even, molecular chain is more regular, thus the forming quality of polyacrylonitrile film is improved, be conducive to follow-up modification is carried out to it after, prepare the various product with different high-performance.Particularly, can adopt two-way stretch simultaneously, first carry out longitudinal stretching and carry out cross directional stretch again, these all belong to common practise and the routine techniques selection of those skilled in the art;

C), obtain polyacrylonitrile film, the thickness of polyacrylonitrile film is 1mm;

Detect through differential scanning calorimeter and thermogravimetric analysis experiment instrument, the fusing point of the polyacrylonitrile film that the present embodiment 1 prepares is 312 DEG C, and its heat decomposition temperature is 259 DEG C.

Further, polyacrylonitrile film obtained above has been carried out the abundant processed and applied of following process modification realization to polyacrylonitrile film by the embodiment of the present invention 1, obtain the various product with different high-performance, and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, specific as follows:

Preferably, in order to ensure the processed and applied effect of polyacrylonitrile film in the present embodiment, before processed and applied is carried out to polyacrylonitrile film, embodiment adds the pretreatment procedure of volume to volume, be specially: under low-temperature heat condition, in the present embodiment, temperature is 130 DEG C, and vacuum deviates from auxiliary agent residual in polyacrylonitrile film.

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt the embodiment of the present invention 1 polyacrylonitrile film obtained above as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile film is carried out pre-oxidation in a heated condition, Heating temperature is less than the fusing point of polyacrylonitrile film, and be greater than the heat decomposition temperature of polyacrylonitrile film, particularly, in the present embodiment, Heating temperature is 300 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, respectively through cyclisation, preoxidised polyacrylonitrile film is obtained after dehydrogenation, preferably, preoxidised polyacrylonitrile film to be carried out 1 time or repeatedly (as 1-10 time) rolls, make preoxidised polyacrylonitrile film finer and close, particularly, in the present embodiment, carry out 5 times to preoxidised polyacrylonitrile film to roll, after testing, the heatproof temperature of preoxidised polyacrylonitrile film is 300 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments, and materials'use cost is low.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 1, wherein, end temp during first stage formula heats up is 1800 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, preferably, to to carry out 1 time in the heat insulation graphite film of random stratiform or repeatedly (as 1-10 time) rolls, make the heat insulation graphite film in random stratiform finer and close, particularly, in the present embodiment, carry out 5 times to the heat insulation graphite film in random stratiform to roll, adopt four probe method to detect the resistivity (higher) of conductive graphite film, then obtain thermal conductivity by formulae discovery, after testing, the thermal conductivity of heat insulation graphite film is about 10W/mk, there is heat insulation good characteristic, can be used as high efficiency heat insulation material, and materials'use cost is low.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 1 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3200 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, preferably, to to carry out 1 time in the conductive graphite film of regular stratiform or repeatedly (as 1-10 time) rolls, make the conductive graphite film in regular stratiform finer and close, particularly, in the present embodiment, carry out 5 times to the conductive graphite film in regular stratiform to roll, four probe method is adopted to detect the face phase resistance rate (namely low) of conductive graphite film, then obtain plane thermal conductivity by formulae discovery, after testing, the plane thermal conductivity of conductive graphite film is 1500W/mk, there is very superior heat conduction and conductivity, and materials'use cost is low.

Embodiment 2:

In the present embodiment 2, all the other are identical with embodiment 1 for the preparation process of polyacrylonitrile film, and difference is only:

A), by the polyacrylonitrile of 60wt% and the auxiliary agent of 40wt% blended, wherein, polyacrylonitrile is the acrylonitrile monemer adopting 92wt%, the copolymerized polymer that the second comonomer of 5wt% and the Third monomer of 3wt% prepare after polyreaction, Third monomer is selected from methylene-succinic acid, sodium allylsulfonate, methylpropene sodium sulfonate, methacrylic benzene sulfonic acid sodium salt, vinyl pyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl are for any one in amino ethyl ester, particularly, in the present embodiment, Third monomer is sodium allylsulfonate, auxiliary agent comprises the solvent of 60wt%, the thickening material of 30wt% and the water of 10wt%, detect through differential scanning calorimeter, the melt temperature of material system is 180 DEG C,

In step b), adjust the phase temperature melt extruded in technique in stage intensification type of heating, the setting of concrete phase temperature can specifically be selected according to the actual requirements, wherein, the top temperature of phase temperature is greater than the melt temperature of material system, after testing, the melt strength of the material system in present embodiment is 1.22 × 10 ⁵pa.s.

In step c), detect through differential scanning calorimeter and thermogravimetric analysis experiment instrument, the fusing point of the polyacrylonitrile film that the present embodiment 2 prepares is 310 DEG C, and its heat decomposition temperature is 269 DEG C.

Further, polyacrylonitrile film obtained above has been carried out the abundant processed and applied of following process modification realization to polyacrylonitrile film by the embodiment of the present invention 2, obtain the various product with different high-performance, and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, all the other are identical with embodiment 1, and difference is only:

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt the embodiment of the present invention 2 polyacrylonitrile film obtained above as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile film is carried out pre-oxidation under the heating condition of 280 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, obtain preoxidised polyacrylonitrile film respectively through after cyclisation, dehydrogenation, then 5 times are carried out to preoxidised polyacrylonitrile film and roll; After testing, the heatproof temperature of preoxidised polyacrylonitrile film is 220 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 2, wherein, end temp during first stage formula heats up is 1600 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the heat insulation graphite film in random stratiform and roll; After testing, the thermal conductivity of heat insulation graphite film is about 6W/mk, has heat insulation good characteristic, can be used as high efficiency heat insulation material.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 2 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3500 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the conductive graphite film in regular stratiform and roll; After testing, the plane thermal conductivity of conductive graphite film is 1600W/mk, has very superior heat conduction and conductivity.

Embodiment 3:

In the present embodiment 3, all the other are identical with embodiment 1 for the preparation process of polyacrylonitrile film, and difference is only:

A), by the polyacrylonitrile of 90wt% and the auxiliary agent of 10wt% blended, wherein, polyacrylonitrile adopts the homopolymer polymer for preparing after polyreaction of acrylonitrile monemer, and auxiliary agent comprises the water of the solvent of 65wt%, the thickening material of 5wt% and 30wt%; Detect through differential scanning calorimeter, the melt temperature of material system is 238 DEG C;

In step b), adjust the phase temperature melt extruded in technique in stage intensification type of heating, the setting of concrete phase temperature can specifically be selected according to the actual requirements, wherein, the top temperature of phase temperature is greater than the melt temperature of material system, after testing, the melt strength of the material system in present embodiment is 1.48 × 10 ⁵pa.s.

In step c), detect through differential scanning calorimeter and thermogravimetric analysis experiment instrument, the fusing point of the polyacrylonitrile film that the present embodiment 3 prepares is 319 DEG C, and its heat decomposition temperature is 255 DEG C.

Further, polyacrylonitrile film obtained above has been carried out the abundant processed and applied of following process modification realization to polyacrylonitrile film by the embodiment of the present invention 3, obtain the various product with different high-performance, and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, all the other are identical with embodiment 1, and difference is only:

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt the embodiment of the present invention 3 polyacrylonitrile film obtained above as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile film is carried out pre-oxidation under the heating condition of 310 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, obtain preoxidised polyacrylonitrile film respectively through after cyclisation, dehydrogenation, then 5 times are carried out to preoxidised polyacrylonitrile film and roll; After testing, the heatproof temperature of preoxidised polyacrylonitrile film is 500 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 3, wherein, end temp during first stage formula heats up is 2000 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the heat insulation graphite film in random stratiform and roll; After testing, the thermal conductivity of heat insulation graphite film is about 18W/mk, has heat insulation good characteristic, can be used as high efficiency heat insulation material.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 3 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3000 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the conductive graphite film in regular stratiform and roll; After testing, the plane thermal conductivity of conductive graphite film is 1200W/mk, has very superior heat conduction and conductivity.

Embodiment 4:

In the present embodiment 4, all the other are identical with embodiment 1 for the preparation process of polyacrylonitrile film, and difference is only:

A), by the polyacrylonitrile of 80wt% and the auxiliary agent of 20wt% blended, wherein, polyacrylonitrile adopts the homopolymer polymer for preparing after polyreaction of acrylonitrile monemer, and auxiliary agent comprises the solvent of 100wt%; Detect through differential scanning calorimeter, the melt temperature of material system is 225 DEG C;

In step b), after testing, the melt strength of the material system in present embodiment is 1.35 × 10 ⁵pa.s.

In step c), detect through differential scanning calorimeter and thermogravimetric analysis experiment instrument, the fusing point of the polyacrylonitrile film that the present embodiment 4 prepares is 315 DEG C, and its heat decomposition temperature is 252 DEG C.

Further, polyacrylonitrile film obtained above has been carried out the abundant processed and applied of following process modification realization to polyacrylonitrile film by the embodiment of the present invention 4, obtain the various product with different high-performance, and then be applied to different industrial fields, because the cost of polyacrylonitrile raw material is low, thus be greatly beneficial to the manufacture optimization of multiple industrial field and fall this, all the other are identical with embodiment 1, and difference is only:

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt the embodiment of the present invention 4 polyacrylonitrile film obtained above as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile film is carried out pre-oxidation under the heating condition of 260 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, obtain preoxidised polyacrylonitrile film respectively through after cyclisation, dehydrogenation, then 5 times are carried out to preoxidised polyacrylonitrile film and roll; After testing, the heatproof temperature of preoxidised polyacrylonitrile film is 250 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 4, wherein, end temp during first stage formula heats up is 1800 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the heat insulation graphite film in random stratiform and roll; After testing, the thermal conductivity of heat insulation graphite film is about 9W/mk, has heat insulation good characteristic, can be used as high efficiency heat insulation material.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 4 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3200 DEG C, particularly, the speed of stage intensification can be selected according to the actual requirements, also specifically see the carburizing reagent step of Kapton, then 5 times can be carried out to the conductive graphite film in regular stratiform and roll; After testing, the plane thermal conductivity of conductive graphite film is 1500W/mk, has very superior heat conduction and conductivity.

Embodiment 5:

In the present embodiment 5, all the other are identical with embodiment 1 for the preparation process of polyacrylonitrile film, and difference is only: do not comprise and perform step c0 in above-described embodiment 1) described in two-way stretch process is carried out to the polyacrylonitrile film that step b) obtains.

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt the embodiment of the present invention 5 polyacrylonitrile film obtained above as raw material, preoxidised polyacrylonitrile film is obtained after polyacrylonitrile film is carried out pre-oxidation in a heated condition, Heating temperature is less than the fusing point of polyacrylonitrile film, and be greater than the heat decomposition temperature of polyacrylonitrile film, particularly, in the present embodiment, Heating temperature is 300 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, respectively through cyclisation, preoxidised polyacrylonitrile film is obtained after dehydrogenation, then carry out 5 times to preoxidised polyacrylonitrile film to roll, after testing, the heatproof temperature of preoxidised polyacrylonitrile film is 240 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments, and materials'use cost is low.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 5, wherein, end temp during first stage formula heats up is 1800 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, then carry out 5 times to the heat insulation graphite film in random stratiform to roll, adopt four probe method to detect the resistivity (higher) of conductive graphite film, then obtain thermal conductivity by formulae discovery, after testing, the thermal conductivity of heat insulation graphite film is about 19W/mk, there is heat insulation good characteristic, can be used as high efficiency heat insulation material, and materials'use cost is low.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 5 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3200 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, then carry out 5 times to the conductive graphite film in regular stratiform to roll, four probe method is adopted to detect the face phase resistance rate (namely low) of conductive graphite film, then obtain plane thermal conductivity by formulae discovery, after testing, the plane thermal conductivity of conductive graphite film is 1200W/mk, there is very superior heat conduction and conductivity, and materials'use cost is low.

Embodiment 6:

A kind of preparation method of preoxidised polyacrylonitrile film, wherein, adopt polyacrylonitrile fibre cloth as raw material, this polyacrylonitrile fibre cloth adopts polyacrylonitrile protofibril cloth through coating or infiltrates polyacrylonitrile solution and obtain after drying, particularly, polyacrylonitrile in polyacrylonitrile solution, effectively by the gap-fill of polyacrylonitrile protofibril cloth, makes the polyacrylonitrile fibre cloth that finally obtains finer and close.Further particularly, polyacrylonitrile protofibril cloth can be woven, also can be non-woven fabrics (making as adopted electrostatic spinning).Preoxidised polyacrylonitrile film is obtained after polyacrylonitrile fibre cloth is carried out pre-oxidation in a heated condition, Heating temperature is less than the fusing point of polyacrylonitrile fibre cloth and is greater than the heat decomposition temperature of polyacrylonitrile fibre cloth, particularly, in the present embodiment, Heating temperature is 300 DEG C, this pre-oxidation formula refers to Fig. 2, in pre-oxidation process, polyacrylonitrile film in a heated condition, obtain preoxidised polyacrylonitrile film respectively through after cyclisation, dehydrogenation, then 5 times are carried out to preoxidised polyacrylonitrile film and roll; After testing, the heatproof temperature of preoxidised polyacrylonitrile film is 200 DEG C, has the good characteristic of fire-retardant, heatproof, resistance to chemical attack, can be used as the protective clothing material of firefighter, also can as the protective material of operator under harsh environments, and materials'use cost is low.

A kind of preparation method of heat insulation graphite film, wherein, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film obtained above for the embodiment of the present invention 6, wherein, end temp during first stage formula heats up is 1800 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, then carry out 5 times to the heat insulation graphite film in random stratiform to roll, adopt four probe method to detect the resistivity (higher) of conductive graphite film, then obtain thermal conductivity by formulae discovery, after testing, the thermal conductivity of heat insulation graphite film is about 20W/mk, there is heat insulation good characteristic, can be used as high efficiency heat insulation material, and materials'use cost is low.

A kind of preparation method of conductive graphite film, wherein, carry out greying under the heating condition heated up at second-order segmentation by heat insulation graphite film in random stratiform obtained above for the embodiment of the present invention 6 and be obtained by reacting conductive graphite film in regular stratiform, wherein, end temp during second-order segmentation heats up is 3200 DEG C, particularly, its starting temperature, the speed of the soaking time under phase temperature and stage intensification can be selected according to the actual requirements, also can specifically see the carburizing reagent step of Kapton, then carry out 5 times to the conductive graphite film in regular stratiform to roll, four probe method is adopted to detect the face phase resistance rate (namely low) of conductive graphite film, then obtain plane thermal conductivity by formulae discovery, after testing, the plane thermal conductivity of conductive graphite film is 1000W/mk, there is very superior heat conduction and conductivity, and materials'use cost is low.

Can find out from the implementation result of the above embodiment of the present invention, when adopting polyacrylonitrile film as polyacrylonitrile base material, preparing in polyacrylonitrile thin-film process, carried out c0) described in the polyacrylonitrile film that step b) is obtained carry out two-way stretch process after the implementation result of polyacrylonitrile film that obtains will significantly better than not carrying out step c0) the polyacrylonitrile film that directly obtains; And adopting polyacrylonitrile film better as the implementation result of polyacrylonitrile base material than adopting polyacrylonitrile fibre cloth as polyacrylonitrile base material, this is because the density of polyacrylonitrile film is better than polyacrylonitrile fibre cloth.

Comparative example 1:

This comparative example 1 adopts publication number wherein a kind of embodiment of soluble polyacrylic cyanide composite disclosed in CN100999604A to prepare polyacrylonitrile film, and after testing, the fusing point of polyacrylonitrile film is 150 DEG C, and its heat decomposition temperature is 270 DEG C.

Disclosed in reference above-described embodiment 1, the processed and applied method of polyacrylonitrile film carries out processed and applied to the polyacrylonitrile film that this comparative example 1 prepares, in pre-oxidation process, when Heating temperature arrives 150 DEG C, polyacrylonitrile film generation melting phenomenon, cannot realize pre-oxidation.

Comparative example 2:

This comparative example 2 adopts publication number, and disclosed in CN101323656A, embodiment 10 is as polyacrylonitrile film, and after testing, the fusing point of polyacrylonitrile film is 205 DEG C, and its heat decomposition temperature is 328 DEG C.

Disclosed in reference above-described embodiment 1, the processed and applied method of polyacrylonitrile film carries out processed and applied to the polyacrylonitrile film that this comparative example 1 prepares, in pre-oxidation process, when Heating temperature arrives 205 DEG C, polyacrylonitrile film generation melting phenomenon, cannot realize pre-oxidation.

Comparative example 3:

This comparative example 3 adopts the water of the polyacrylonitrile of 55wt% and 45wt% blended as material system, all the other are see the polyacrylonitrile method for manufacturing thin film described in this above-described embodiment 1, and when carrying out melt extruding technique, for the vaporization at processing temperatures of anti-sealing, pressurization is adopted to melt the shaping method that then reduces pressure, operate very complicated, after testing, the melt temperature of material system is 232 DEG C; The melt strength of material system is 1.15 × 10 ⁵pa.s; The fusing point of polyacrylonitrile film is 315 DEG C, and its heat decomposition temperature is 250 DEG C; And steam bubble on the polyacrylonitrile film that obtains of this comparative example 3 is too much, cannot carry out following process application at all.Comparative example 4:

This comparative example 4 adopts the spinning solution used in solvent spinning working method as material system, and see the polyacrylonitrile method for manufacturing thin film described in this above-described embodiment 1, after testing, the melt temperature of material system is 153 DEG C; The melt strength of material system is 1 × 10 ⁴pa.s; Because melt strength is too low, cause material system after melt extruding art breading, at all cannot the polyacrylonitrile film of extrusion moulding.

Comparative example 5:

This comparative example 5 adopts polyacrylonitrile protofibril cloth as polyacrylonitrile base material, after testing, the fusing point of polyacrylonitrile protofibril cloth is 300 DEG C, and its heat decomposition temperature is 255 DEG C.

Disclosed in reference above-described embodiment 1, the processed and applied method of polyacrylonitrile film carries out processed and applied to the polyacrylonitrile protofibril cloth that this comparative example 5 prepares, after testing, the heatproof temperature of preoxidised polyacrylonitrile film is 100 DEG C, the thermal conductivity of heat insulation graphite film is about 200W/mk, the plane thermal conductivity of conductive graphite film is 700W/mk, all can not reach the Essential Performance Requirements of each product.

Can learn through above-described embodiment, the method that the embodiment of the present invention provides efficiently solves the two large conflicting technological difficulties that polyacrylonitrile material exists: namely when being prepared polyacrylonitrile film by melt-processed, need the fusing point reducing polyacrylonitrile raw material, and make its fusing point be less than its heat decomposition temperature, thus guarantee to obtain polyacrylonitrile film, and when the application of concrete industry is carried out to polyacrylonitrile film, need again to carry out processing modified could realization to polyacrylonitrile film, iff the simple fusing point reducing polyacrylonitrile raw material in order to prepare polyacrylonitrile film, obviously this polyacrylonitrile film prepared can be caused again cannot to carry out concrete industry application, also or need by very complicated, and the technology being difficult to realize is carried out polyacrylonitrile film and is again processed, the fusing point of polyacrylonitrile film just can be made higher than its heat decomposition temperature, thus without actual application value, and present inventor made a concrete analysis of these technological difficulties and cause these technological difficulties to occur essential reason after, propose to adopt the solvent being applicable to mass parts to dissolve polyacrylonitrile, guarantee the melt temperature reducing with polyacrylonitrile the material system being main component, guarantee that again this material system is melt extruding the melt strength in technological process, owing to melt extruding in the process of cooling in technological process, because most of solvent is volatilized, namely ensure that the fusing point of the polyacrylonitrile film prepared is higher than its heat decomposition temperature, namely two above-mentioned large conflicting technological difficulties are efficiently solved.

The embodiment of the present invention further optimally, water adding thickening material and dissolve each other with thickening material in material system etc. is as the auxiliary agent of material system, and then can the interpolation mass parts of solvent be controlled in less scope, thus guarantee that material system is melt extruding the melt strength in technological process, finally obtain the polyacrylonitrile film being applicable to carrying out following process, thickness is 0.025-3mm.Particularly, when the solvent added is less, the polyacrylonitrile in material system is in solvent swelling state mostly, therefore can add the thickening material of small amount and the water of more amount reduces the melt temperature of material system further as auxiliary agent; When the solvent added is more, polyacrylonitrile in material system is in and dissolves completely or basic dissolved state completely, therefore can add the thickening material of more amount and the water of small amount to improve material system further as auxiliary agent and melt extruding the melt strength in technological process, on this principle basis, the interpolation mass parts of various auxiliary agent can specifically be selected according to actual needs, and the present embodiment does not do and specifically launches to describe.

It should be noted that, all kinds of physical parametric data involved by this patent full text are all the test results obtained after testing after the country or industry standard or the usual detection means of industry that reference is relevant, the concrete detection means of these physical parameters or step are the common practise of those skilled in the art, therefore specifically do not launch to carry out word herein one by one and repeat.

To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.

In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.

Claims

1. the preparation method of a preoxidised polyacrylonitrile film, it is characterized in that, adopt polyacrylonitrile base material as raw material, preoxidised polyacrylonitrile film is obtained after described polyacrylonitrile base material is carried out pre-oxidation in a heated condition, described Heating temperature is less than the fusing point of described polyacrylonitrile base material and is greater than the heat decomposition temperature of polyacrylonitrile base material, the heatproof temperature of described preoxidised polyacrylonitrile film is 200-500 DEG C, wherein, the thickness of described polyacrylonitrile base material is 0.025-3mm, and the fusing point of described polyacrylonitrile base material is greater than its heat decomposition temperature;

When described polyacrylonitrile base material is polyacrylonitrile film, the preparation method of described polyacrylonitrile film comprises following operation steps:

2. the preparation method of preoxidised polyacrylonitrile film as claimed in claim 1, it is characterized in that, described auxiliary agent comprises the thickening material of 1-30wt%, described thickening material is selected from any one or a few mixing of polyoxyethylene glycol, polyvinyl alcohol, hydroxylated cellulose, polyacrylamide, for improving the melt strength of material system;

3. the preparation method of preoxidised polyacrylonitrile film as claimed in claim 1, is characterized in that, at described step b) complete after, step c) carry out before, also comprise:

C0), to described step b) the polyacrylonitrile film that obtains carries out two-way stretch process.

4. the preparation method of preoxidised polyacrylonitrile film as claimed in claim 1, is characterized in that, described step b) specifically comprise:

B50), cooled form film is passed through pull roll assembly rolling.

5. the preparation method of preoxidised polyacrylonitrile film as claimed in claim 4, is characterized in that, described refrigerating unit/and described pull roll assembly are placed in enclosed space, and described enclosed space is marked with steam, and the composition of described steam comprises auxiliary agent.

6. the preparation method of preoxidised polyacrylonitrile film as claimed in claim 1, it is characterized in that, described polyacrylonitrile base material is polyacrylonitrile fibre cloth, and described polyacrylonitrile fibre cloth adopts polyacrylonitrile protofibril cloth through coating or infiltrates polyacrylonitrile solution and obtain after drying.

7. a preoxidised polyacrylonitrile film, is characterized in that, described preoxidised polyacrylonitrile film adopts the preparation method of the preoxidised polyacrylonitrile film as described in claim 1-6 any one to prepare.

8. the preparation method of a heat insulation graphite film, it is characterized in that, the heat insulation graphite film that carburizing reagent obtains in random stratiform is carried out under the heating condition heated up in first stage formula by preoxidised polyacrylonitrile film as claimed in claim 7, wherein, the end temp in described first stage formula intensification is 1600-2000 DEG C; The thermal conductivity of described heat insulation graphite film is equal to or less than 20W/mk.

9. a heat insulation graphite film, is characterized in that, described heat insulation graphite film adopts the preparation method of heat insulation graphite film as claimed in claim 8 to prepare.

10. the preparation method of a conductive graphite film, it is characterized in that, is carried out greying under the heating condition that heat insulation graphite film as claimed in claim 9 in random stratiform is heated up at second-order segmentation and be obtained by reacting conductive graphite film in regular stratiform, wherein, the end temp in described second-order segmentation intensification is 3000-3500 DEG C; The plane thermal conductivity of described conductive graphite film is 1000-1600W/mk.

11. 1 kinds of conductive graphite films, is characterized in that, described conductive graphite film adopts the preparation method of conductive graphite film as claimed in claim 10 to prepare.