CN104846466A

CN104846466A - High thermal conductivity polyacrylonitrile fiber and preparation method thereof

Info

Publication number: CN104846466A
Application number: CN201510164719.3A
Authority: CN
Inventors: 陆炅; 毛惠敏; 石建华
Original assignee: ZHEJIANG TAISUO TECHNOLOGY Co Ltd
Current assignee: ZHEJIANG TAISUO TECHNOLOGY Co Ltd
Priority date: 2015-04-09
Filing date: 2015-04-09
Publication date: 2015-08-19
Anticipated expiration: 2035-04-09
Also published as: CN104846466B

Abstract

The present invention relates to a high thermal conductivity polyacrylonitrile fiber and a preparation method thereof. The high thermal conductivity polyacrylonitrile fiber is prepared by adding graphene concentrate to uniformly disperse the graphene in polyacrylonitrile spinning stock solution, and conducting wet spinning on the stock solution. The method is as below: treating ultrafine graphene by magnetic field and ultrasonic in an aqueous solution of aqueous titanate; then distilling in the magnetic field to obtain a graphene concentrate; respectively adding the monomer, an initiator and a graphene concentrate into a solvent for a heating polymerization reaction to obtain a polyacrylonitrile spinning stock solution; and finally subjecting the obtained polyacrylonitrile spinning stock to wet spinning to obtain the high thermal conductivity polyacrylonitrile fiber. The high thermal conductivity polyacrylonitrile fiber contains uniformly dispersed specially treated ultrafine graphene, and the treated graphene can be well combined with the polyacrylonitrile, thereby significantly improving the thermal performance of polyacrylonitrile.

Description

A kind of high heat conduction polyacrylonitrile fibre and preparation method thereof

Technical field

The invention belongs to polyacrylonitrile fibre preparing technical field, relate to a kind of high heat conduction polyacrylonitrile fibre and preparation method thereof, particularly relate to a kind of polyacrylonitrile spinning solution processed Graphene concentrate being added to obtained graphene uniform dispersion in acrylonitrile polymerization process, and carry out the preparation method of the obtained high heat conduction polyacrylonitrile fibre of wet spinning operation with polyacrylonitrile spinning solution.

Background technology

Polyacrylonitrile fibre is one of large kind of synthetic fiber four, and its output is only second to polyester fiber and polyamide fiber in synthetic fiber, and global output has reached 3,000,000 tons/year.Polyacrylonitrile fibre is a kind of excellent textile product raw material, and fiber is fast light, radioresistance, softness, warming, is described as " artificial wool ", is widely used in the field of textiles such as garment material, tarpaulin, curtain.But, along with people's living standard to improve constantly with clothing design growing, warming is no longer the unitary request of clothes, people to its comfort level, functional and security requirement is more and more higher.Insulation garment can stop human heat outwards to discharge when temperature is lower, thus reach warming effect, but in the summer that temperature is higher, this clothes will lose its effect, so, if a kind of clothes that can promote thermal release can be invented, effectively will solve the clothes problem of hot weather, make people more comfortable in the face of hot weather.

Another main application of polyacrylonitrile fibre is for preparing carbon fiber, and carbon fiber obtains extensive use in every field that is military and civilian industry with its outstanding mechanical performance.From civilian industries such as space flight, aviation, automobile, electronics, machinery, chemical industry, light textiles to sports equipment and leisure goods etc.The use approach of current carbon fiber mainly can for the industrial circles such as military industry field, wind power generation blade such as aircraft manufacturing, electromagnetic shielding except the health such as electric material, artificial ligament substitute material and for the manufacture of rocket envelope, power ship, industrial robot, leaf springs of car and the sports field such as driving shaft, baseball to be complex as main carbon fiber reinforced composite with other materials, so carbon fiber is the infant industry material in typical high-tech area.Carbon fiber with other materials compound after, its outstanding physical property and chemical property can only some embody in the composite, in order to the better carbon fibre composite of processability, the performance promoting carbon fiber from source becomes a kind of effective solution.

Patent of invention CN 103484966 A describes a kind of preparation method with the polyacrylonitrile fibre of anti-flammability, and this invention is by adding fire retardant when preparing polyacrylonitrile fibre spinning solution and making final polyacrylonitrile fibre have certain anti-flammability through special process process.Polyacrylonitrile, acrylonitrile and phosphonium flame retardant first carry out mixing and carry out freezing, irradiation, the operation such as polymerization and washing to mixture again by this invention, finally obtained spinning solution carries out spinning and obtains flame-resistant polyacrylonitrile fiber, the method technique is more complicated, and fire retardant is not through special treatment, this causes the fibre strength of final fiber product to decline to a great extent with regard to being easy to.

Summary of the invention

The present invention relates to a kind of high heat conduction polyacrylonitrile fibre and preparation method thereof, particularly provide a kind of Graphene concentrate of adding when acrylonitrile carries out polymerisation graphene uniform is dispersed in polyacrylonitrile spinning solution and carries out high heat conduction polyacrylonitrile fibre prepared by wet spinning and preparation method thereof to stoste.The present invention first by superfine graphite alkene in the aqueous solution of aqueous titanic acid ester through magnetic field, ultrasonic process, carry out again distilling obtained Graphene concentrate in magnetic field, monomer, initator and Graphene concentrate are joined in solvent respectively and carries out heated polymerizable reaction, reaction terminates rear obtained polyacrylonitrile spinning solution, finally carries out wet spinning to spinning solution and obtains high heat conduction polyacrylonitrile fibre.Containing the homodisperse superfine graphite alkene through special treatment in described high heat conduction polyacrylonitrile fibre, the Graphene processed well can be combined with polyacrylonitrile, thus significantly improves the heat conductivility of polyacrylonitrile.

The preparation method of a kind of high heat conduction polyacrylonitrile fibre of the present invention, carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, obtained the polyacrylonitrile spinning solution of graphene-containing by in-situ polymerization, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology;

The preparation method of described Graphene concentrate: be first dissolved in water by aqueous titanic acid ester, then adds superfine graphite alkene powder, carries out ultrasonic disperse, namely obtain graphene dispersing solution in magnetic field; Then under additional magnetic fields, graphene dispersing solution is carried out distilling or decompression distillation, namely obtain Graphene concentrate.

As preferred technical scheme:

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, the concrete steps of in-situ polymerization are: monomer, initator, Graphene concentrate are added respectively in solvent, mix and make polymeric solution; Under normal pressure 50 ~ 70 DEG C of temperature conditions, be polymerized 2 ~ 5h, monomer conversion is 70 ~ 85%, obtains polyacrylonitrile spinning solution; Described monomer at least comprises the first monomer, and the first described monomer is acrylonitrile;

The mass concentration of monomer in polymeric solution is 10 ~ 35%, and the mass percent of initator relative monomer is 0.5 ~ 1.5%, and the mass percent of Graphene concentrate relative monomer is 0.7 ~ 33%.

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, described monomer is except comprising the first monomer, also comprise second comonomer, described second comonomer is the one in acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate; The mass fraction of the relative total monomer of the first monomer is 80 ~ 99%, and the mass fraction of the relative total monomer of second comonomer is 1 ~ 20%.

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, described monomer comprises the first monomer, second comonomer and Third monomer, and described Third monomer is that itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, dimethylaminoethyl acrylate methyl are for the one in amino ethyl ester; The mass fraction of the relative total monomer of the first monomer is 80 ~ 98%, and the mass fraction of the relative total monomer of second comonomer is 1 ~ 17%, and the mass fraction of the relative total monomer of Third monomer is 1 ~ 3%.

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, described initator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate; Described solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate.

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, the mass fraction of described graphene powder in described graphene dispersing solution is 0.5 ~ 8%, the quality of described aqueous titanic acid ester is less than or equal to 2% of graphene powder quality, and in described Graphene concentrate, the mass fraction of Graphene is 30-70%;

Described aqueous titanic acid ester is Di(dioctylpyrophosphato) ethylene titanate, or the chelate solution of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine, or two (dioctylphyrophosphoric acid ester) oxyacetate titanate esters, or two (dioctyl diethanol) ethylenediamine titanate esters, or two (octyl phenol polyoxyethylene ether) phosphide, aqueous titanic acid ester contains hydrolyzable lower alkyloxy and titanate esters fully can be combined with Graphene with the double bond generation chemical reaction of Graphene, play the effect of finishing, superfine graphite alkene is made to have higher activity.；

The process of described dissolving is by churned mechanically mode, and rotating speed is 50 ~ 100 revs/min, and mixing time is 5 ~ 30 minutes, temperature is 10 ~ 35 DEG C, aqueous titanic acid ester can dissolve each other with water, and we accelerate titanate esters dissolution velocity by stirring at low speed, significantly shorten dissolution time;

Described superfine graphite alkene powder is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 6 ~ 10 nanometers; In described Graphene concentrate, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer.The granularity of Graphene is less, and corresponding specific area is larger, and the Graphene of small particle size is more conducive to playing the outstanding mechanical performance of Graphene and other physical properties, and can also reduce the use amount of Graphene in use;

Magnetic field intensity corresponding to described ultrasonic disperse magnetic field is 0.5 ~ 5T; The magnetic field intensity of described externally-applied magnetic field is 2 ~ 6T, ink alkene material has special structural form, in magnetic field, Graphene in graphene dispersing solution can produce orderly aligning, in concentration process, because the content of Graphene raises gradually, the viscosity of Graphene concentrate can become large gradually, therefore, the ordered arrangement of Graphene is controlled by the magnetic field of higher magnetic field intensity;

The ultrasonic frequency of described ultrasonic disperse is 20 ~ 30KHz, power is 1 ~ 5 kilowatt, the ultrasonic disperse time is 30 ~ 90 minutes, it is 10 ~ 60 DEG C that temperature controls, ultrasonic disperse has good effect to the dispersion of Graphene in dispersion liquid, also graphenic surface can be made fully to be modified by aqueous titanic acid ester, in addition, Graphene is aligned in graphene dispersing solution by magnetic fields thus after reaching a poised state, due to ultrasonic high-frequency effect, thus this poised state is broken, by continuous mechanical function, distance between graphene sheet layer is increased, thus reach the effect of stripping,

Described distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 80 ~ 100 DEG C, and distillation time is 10 ~ 60 minutes;

The parameter of described decompression distillation is: vacuum is-0.01MPa ~-0.1MPa, vapo(u)rizing temperature is 50 ~ 80 DEG C, distillation time is 10 ~ 30 minutes, by distillation or decompression distillation, the water evaporates in graphene dispersing solution is made to be separated and Graphene content is increased substantially, moisture content significantly reduces, and effectively improves the production and processing problem because moisture content too much causes;

The preparation method of a kind of high heat conduction polyacrylonitrile fibre as above, described wet spinning technology is: spinning solution is extruded through spinning head and entered coagulating bath, and then enter pre-heating bath, rinsing bowl and stretch bath successively, in drying machine, compacting by drying is carried out again after oiling, carry out steam heat sizing through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2 ~ 0.3MPa, shaping time 10 ~ 30 minutes, tow, again through oiling and compacting by drying process, obtains high heat conduction polyacrylonitrile fibre;

Described coagulating bath is the aqueous solution containing corresponding solvent dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate mass fraction 30 ~ 40%, temperature 20 ~ 30 DEG C, containing the solvent identical with polymerization technique in coagulating bath, make fibre bundle can be shaping sooner;

Described pre-heating bath is the sulfosalt surfactant aqueous solution containing the corresponding solvent dimethylformamide of mass fraction 5 ~ 10%, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate and 2%, temperature 60 ~ 65 DEG C, surfactant effectively can improve the surface of fibre bundle;

The water temperature of described rinsing bowl 50 ~ 65 DEG C, carrys out the impurity on cleaning fiber bundle surface by this step;

Described stretch bath is the water containing 2% sulfosalt surfactant, temperature 95 ~ 98 DEG C, and high temperature and surfactant can make fiber have better ductility;

Spinning head extruded velocity 0.5 ~ 1m/min, draw ratio 5 ~ 7 times.

Described sulfosalt surfactant is dioctyl succinate disulfonate acid, neopelex or sodium glycocholate.

The high heat conduction polyacrylonitrile fibre of the one that the present invention also proposes to be obtained by above preparation method, containing the superfine graphite alkene of 0.5 ~ 15% in described high heat conduction polyacrylonitrile fibre; The thermal conductivity factor of described high heat conduction polyacrylonitrile fibre is 1 ~ 5W/mk.

As preferred technical scheme:

The high heat conduction polyacrylonitrile fibre of one of the present invention, the viscosity average molecular weigh of described polyacrylonitrile is 50,000 ~ 100,000; Described superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer; The filament number of described high heat conduction polyacrylonitrile fibre is 1.0 ~ 3.3dtex, and fracture strength is 2.5 ~ 6.5cN/dtex.

Beneficial effect:

The preparation method of a kind of high heat conduction polyacrylonitrile fibre of the present invention, design is unique, and step is easy, successful.

High heat conduction polyacrylonitrile fibre of the present invention, Conductivity of Fiber is hot good, and mechanical strength is good, and graphene dispersion is even, and the graphene film number of plies is little, and addition is few.Graphene is through the surface treatment of aqueous titanic acid ester, the active group that graphenic surface is introduced can be good at the compatibility and the adhesion that improve Graphene and polyacrylonitrile, thus obtains the high heat conduction polyacrylonitrile fibre that graphene uniform disperses to be combined in polyacrylonitrile fibre.Multi-layer graphene is in the solution by magnetic field and ultrasonic effect, sandwich construction can be destroyed produces few layer or single-layer graphene, few layer or single-layer graphene can better play the outstanding physical characteristic of Graphene or chemical characteristic, further, through the obtained few layer of process or single-layer graphene, multi-layer graphene just means that we significantly can reduce the addition of Graphene in polyacrylonitrile fibre and do not affect the lifting of polyacrylonitrile fibre heat conductivility.The preparation of high heat conduction polyacrylonitrile fibre, solves the problem that some polyacrylonitrile fibre uses field poor radiation, effectively expands the use field of polyacrylonitrile fibre.

The invention solves polyacrylonitrile fibre uses field poor radiation problem at some, by directly adding the Graphene crossed by aqueous titanic acid ester moditied processing in polyacrylonitrile polymerization process, graphene uniform being dispersed in polyacrylonitrile fibre thus reaching the good improvement of polyacrylonitrile fibre heat conductivility.By using special method to process Graphene, the thermal conductivity that effectively can play high heat conduction polyacrylonitrile fibre also significantly reduces the use amount of Graphene; High heat conduction polyacrylonitrile fibre obtained by this method, avoid the decline of polyacrylonitrile fibre mechanical performance, not only obtained polyacrylonitrile fibre has good thermal conductivity, and using carbon fiber obtained by this high heat conduction polyacrylonitrile fibre, its thermal conductivity also can have significant improvement.By solving these technical problems, the use field of polyacrylonitrile fibre is more comprehensive, and the using method of Graphene is more perfect, and therefore, this invention has great use value.

Detailed description of the invention

Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.

Embodiment 1

A preparation method for high heat conduction polyacrylonitrile fibre, first obtained Graphene concentrate, concrete steps are:

First by aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate solubilize in water, the process of dissolving is by churned mechanically mode, rotating speed is 50 revs/min, mixing time is 5 minutes, temperature is 10 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate is 2% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 0.5T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 20KHz, power is 1 kilowatt, the ultrasonic disperse time is 30 minutes, it is 10 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 0.5%, then under the externally-applied magnetic field effect being 2T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 80 DEG C, and distillation time is 10 minutes, the parameter of decompression distillation is: vacuum is-0.01MPaMPa, vapo(u)rizing temperature is 50 DEG C, distillation time is 10 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 30%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: monomers acrylonitrile, initator azodiisobutyronitrile, Graphene concentrate are added respectively in solvent dimethylformamide, mix formation polymeric solution, 2h is polymerized under normal pressure 50 DEG C of temperature conditions, monomers acrylonitrile conversion ratio is 70%, obtain polyacrylonitrile spinning solution, the mass concentration of monomers acrylonitrile in polymeric solution is 10%, the mass percent of initator azodiisobutyronitrile relative monomer acrylonitrile is 0.5%, the mass percent of Graphene concentrate relative monomer acrylonitrile is 2%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl formamide containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl formamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 0.85% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 1W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 2

First by chelate (model 311W) solubilize of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine in water, the process of dissolving is by churned mechanically mode, rotating speed is 100 revs/min, mixing time is 30 minutes, temperature is 35 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of the chelate solution of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is 1.5% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 5T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 30KHz, power is 5 kilowatts, the ultrasonic disperse time is 90 minutes, it is 60 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 8%, then under the externally-applied magnetic field effect being 6T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 100 DEG C, and distillation time is 60 minutes, the parameter of decompression distillation is: vacuum is-0.1MPa, vapo(u)rizing temperature is 80 DEG C, distillation time is 30 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 70%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: monomers acrylonitrile, initator 2,2'-Azobis(2,4-dimethylvaleronitrile), Graphene concentrate are added respectively in solvent dimethyl sulfoxide (DMSO), mix formation polymeric solution, 5h is polymerized under normal pressure 70 DEG C of temperature conditions, monomers acrylonitrile conversion ratio is 85%, obtain polyacrylonitrile spinning solution, the mass concentration of monomers acrylonitrile in polymeric solution is 35%, the mass percent of initator 2,2'-Azobis(2,4-dimethylvaleronitrile) relative monomer acrylonitrile is 1.5%, the mass percent of Graphene concentrate relative monomer acrylonitrile is 15%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl sulfoxide (DMSO) containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl sulphoxide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 14.9% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 5W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 3

First two for aqueous titanic acid ester (dioctylphyrophosphoric acid ester) oxyacetate titanate esters is dissolved in water, the process of dissolving is by churned mechanically mode, rotating speed is 80 revs/min, mixing time is 20 minutes, temperature is 30 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of two (dioctylphyrophosphoric acid ester) the oxyacetate titanate esters of aqueous titanic acid ester is 1.5% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 2T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 10KHz, power is 3 kilowatts, the ultrasonic disperse time is 50 minutes, it is 20 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 6%, then under the externally-applied magnetic field effect being 5T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 90 DEG C, and distillation time is 30 minutes, the parameter of decompression distillation is: vacuum is-0.05MPa, vapo(u)rizing temperature is 60 DEG C, distillation time is 15 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 50%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: add in solvent dimethylacetylamide respectively by the first monomers acrylonitrile and second comonomer acrylamide, initator dibenzoyl peroxide, Graphene concentrate, mix formation polymeric solution, the mass fraction of the relative total monomer acrylonitrile of the first monomers acrylonitrile and acrylamide is 80%, and the mass fraction of the relative total monomer of second comonomer acrylamide is 20%; Polyase 13 h under normal pressure 60 DEG C of temperature conditions, monomers acrylonitrile and acrylamide conversion ratio are 75%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the acrylamide mass concentration in polymeric solution is 15%, the mass percent of initator dibenzoyl peroxide relative monomer acrylonitrile and acrylamide is 0.8%, the mass percent of Graphene concentrate relative monomer is 10%, and spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, is specially:

Spinning solution is extruded through spinning head and is entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath, rinsing bowl and stretch bath successively, coagulating bath is the aqueous solution of the dimethylacetylamide containing mass fraction 30%, and temperature is 20 DEG C; Pre-heating bath to be dimethylacetamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C; The water temperature of rinsing bowl is 50 DEG C; Stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C; In drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 6.67% in this high heat conduction polyacrylonitrile fibre; Superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer; The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2.5W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 4

First two for aqueous titanic acid ester (dioctyl diethanol) ethylenediamine titanate esters is dissolved in water, the process of dissolving is by churned mechanically mode, rotating speed is 60 revs/min, mixing time is 30 minutes, temperature is 10 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of two (dioctyl diethanol) the ethylenediamine titanate esters of aqueous titanic acid ester is 1.8% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 0.9T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 20KHz, power is 2 kilowatts, the ultrasonic disperse time is 50 minutes, it is 20 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 2%, then under the externally-applied magnetic field effect being 3T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 80 DEG C, and distillation time is 60 minutes, the parameter of decompression distillation is: vacuum is-0.1MPa, vapo(u)rizing temperature is 50 DEG C, distillation time is 10 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 40%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: add in solvent sodium sulfocyanate respectively by the first monomers acrylonitrile and second comonomer methyl acrylate, initator dilauroyl peroxide, Graphene concentrate, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 99%, and the mass fraction of the relative total monomer of second comonomer is 1%, 4h is polymerized under normal pressure 55 DEG C of temperature conditions, monomer conversion is 72%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the methyl acrylate mass concentration in polymeric solution is 20%, the mass percent of initator dilauroyl peroxide relative monomer acrylonitrile and methyl acrylate is 1.0%, the mass percent of Graphene concentrate relative monomer acrylonitrile and methyl acrylate is 25%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be sodium sulfocyanate containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 13.9% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4.5W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 5

First aqueous titanic acid ester two (octyl phenol polyoxyethylene ether) phosphide is dissolved in water, the process of dissolving is by churned mechanically mode, rotating speed is 100 revs/min, mixing time is 5 minutes, temperature is 25 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of aqueous titanic acid ester two (octyl phenol polyoxyethylene ether) phosphide is 2% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 0.8T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 25KHz, power is 3 kilowatts, the ultrasonic disperse time is 60 minutes, it is 30 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in described graphene dispersing solution is 8%, then under the externally-applied magnetic field effect being 6T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 90 DEG C, and distillation time is 60 minutes, the parameter of decompression distillation is: vacuum is-0.01MPa, vapo(u)rizing temperature is 50 DEG C, distillation time is 10 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 30%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: the first monomers acrylonitrile and second comonomer methyl methacrylate, initator di-isopropyl peroxydicarbonate, Graphene concentrate are added respectively in solvent dimethylformamide, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 90%, and the mass fraction of the relative total monomer of second comonomer is 10%, 5h is polymerized under normal pressure 60 DEG C of temperature conditions, monomers acrylonitrile and methyl methacrylate conversion ratio are 70%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the methyl methacrylate mass concentration in polymeric solution is 25%, the mass percent of initator di-isopropyl peroxydicarbonate relative monomer acrylonitrile and methyl methacrylate is 1.2%, the mass percent of Graphene concentrate relative monomer acrylonitrile and methyl methacrylate is 12%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl formamide containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl formamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 5.14% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 6

First two for aqueous titanic acid ester (dioctyl diethanol) ethylenediamine titanate esters is dissolved in water, the process of dissolving is by churned mechanically mode, rotating speed is 50 revs/min, mixing time is 5 minutes, temperature is 35 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of two (dioctyl diethanol) the ethylenediamine titanate esters of aqueous titanic acid ester is 0.8% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 0.9T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 30KHz, power is 5 kilowatts, the ultrasonic disperse time is 90 minutes, it is 10 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in described graphene dispersing solution is 0.5%, then under the externally-applied magnetic field effect being 2T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 80 DEG C, and distillation time is 30 minutes, the parameter of decompression distillation is: vacuum is-0.09MPa, vapo(u)rizing temperature is 60 DEG C, distillation time is 30 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 50%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: add in solvent dimethyl sulfoxide (DMSO) respectively by the first monomers acrylonitrile and second comonomer methacrylonitrile, initator azodiisobutyronitrile, Graphene concentrate, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 85%, and the mass fraction of the relative total monomer of second comonomer is 15%., 5h is polymerized under normal pressure 70 DEG C of temperature conditions, monomers acrylonitrile and methacrylonitrile conversion ratio are 80%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the methacrylonitrile mass concentration in polymeric solution is 22%, the mass percent of initator azodiisobutyronitrile relative monomer acrylonitrile and methacrylonitrile is 1.2%, the mass percent of Graphene concentrate relative monomer acrylonitrile and methacrylonitrile is 10%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl sulfoxide (DMSO) containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl sulfoxide (DMSO) containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 6.67% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2.2W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 7

First by chelate (model 311W) solubilize of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine in water, the process of dissolving is by churned mechanically mode, rotating speed is 60 revs/min, mixing time is 30 minutes, temperature is 35 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of the chelate solution of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is 1.5% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 4T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 28KHz, power is 5 kilowatts, the ultrasonic disperse time is 90 minutes, it is 60 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 8%, then under the externally-applied magnetic field effect being 5T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 100 DEG C, and distillation time is 60 minutes, the parameter of decompression distillation is: vacuum is-0.1MPa, vapo(u)rizing temperature is 80 DEG C, distillation time is 30 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 70%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: add in solvent dimethylacetylamide respectively by the first monomers acrylonitrile and second comonomer vinylacetate, initator 2,2'-Azobis(2,4-dimethylvaleronitrile), Graphene concentrate, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 99%, and the mass fraction of the relative total monomer of second comonomer is 1%, 4h is polymerized under normal pressure 65 DEG C of temperature conditions, monomer conversion is 80%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the vinylacetate mass concentration in polymeric solution is 20%, the mass percent of initator 2,2'-Azobis(2,4-dimethylvaleronitrile) relative monomer acrylonitrile and vinylacetate is 1.0%, the mass percent of Graphene concentrate relative monomer acrylonitrile and vinylacetate is 12%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethylacetylamide containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethylacetamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 10.5% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 3.5W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 8

First the chelate solution (model 311W) of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is dissolved in water, the process of dissolving is by churned mechanically mode, rotating speed is 80 revs/min, mixing time is 30 minutes, temperature is 35 DEG C, then add and long and be widely respectively 1 ~ 200 micron, thickness is the graphene powder of 6 ~ 10 nanometers, the quality of the chelate solution of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is 1.5% of graphene powder quality, be carry out ultrasonic disperse in the magnetic field of 3T in magnetic field intensity, the ultrasonic frequency of ultrasonic disperse is 30KHz, power is 5 kilowatts, the ultrasonic disperse time is 90 minutes, it is 60 DEG C that temperature controls, namely graphene dispersing solution is obtained, the mass fraction of graphene powder in graphene dispersing solution is 8%, then under the externally-applied magnetic field effect being 3T in magnetic field intensity, graphene dispersing solution is carried out distilling or decompression distillation, distillation refers to and by heating, moisture is evaporated and make the process that in graphene dispersing solution, Graphene concentration improves, and vapo(u)rizing temperature is 100 DEG C, and distillation time is 60 minutes, the parameter of decompression distillation is: vacuum is-0.1MPa, vapo(u)rizing temperature is 80 DEG C, distillation time is 30 minutes, namely Graphene concentrate is obtained, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, in Graphene concentrate, the mass fraction of Graphene is 70%, and in Graphene concentrate, Graphene is of a size of: long and be widely respectively 1 ~ 200 micron, and thickness is 1 ~ 6 nanometer.

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile and second comonomer acrylamide, Third monomer itaconic acid, initator dilauroyl peroxide, Graphene concentrate adds in solvent sodium sulfocyanate respectively, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 80%, the mass fraction of the relative total monomer of second comonomer is 17%, the mass fraction of the relative total monomer of Third monomer is 3%, 5h is polymerized under normal pressure 60 DEG C of temperature conditions, monomer conversion is 85%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile, acrylamide and the itaconic acid mass concentration in polymeric solution is 10 ~ 35%, initator relative monomer acrylonitrile, the mass percent of acrylamide and itaconic acid is 1.0%, Graphene concentrate relative monomer acrylonitrile, the mass percent of acrylamide and itaconic acid is 10%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be sodium sulfocyanate containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 8.24% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2.8W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 9

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile, second comonomer methyl acrylate and Third monomer sodium allylsulfonate, initator dilauroyl peroxide, Graphene concentrate adds in solvent dimethylformamide respectively, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 98%, the mass fraction of the relative total monomer of second comonomer is 1%, the mass fraction of the relative total monomer of Third monomer is 1%, polyase 13 h under normal pressure 65 DEG C of temperature conditions, monomers acrylonitrile, methyl acrylate and sodium allylsulfonate conversion ratio are 75%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile, methyl acrylate and the sodium allylsulfonate mass concentration in polymeric solution is 25%, initator dilauroyl peroxide relative monomer acrylonitrile, the mass percent of methyl acrylate and sodium allylsulfonate is 1.2%, the mass percent of Graphene concentrate relative monomer is 15%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl formamide containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl formamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 14% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4.7W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 10

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile, second comonomer methacrylonitrile and Third monomer methylpropene sodium sulfonate, initator dibenzoyl peroxide, Graphene concentrate adds in solvent dimethyl sulfoxide (DMSO) respectively, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 88%, the mass fraction of the relative total monomer of second comonomer is 10%, the mass fraction of the relative total monomer of Third monomer is 2%, 2h is polymerized under normal pressure 70 DEG C of temperature conditions, monomers acrylonitrile, methacrylonitrile and methylpropene sodium sulfonate conversion ratio are 72%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile, methacrylonitrile and the methylpropene sodium sulfonate mass concentration in polymeric solution is 25%, initator dibenzoyl peroxide relative monomer acrylonitrile, the mass percent of methacrylonitrile and methylpropene sodium sulfonate is 1.0%, Graphene concentrate relative monomer acrylonitrile, the mass percent of methacrylonitrile and methylpropene sodium sulfonate is 12%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethyl sulfoxide (DMSO) containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethyl sulfoxide (DMSO) containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 11.7% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 11

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile, second comonomer acrylamide and Third monomer metering system benzene sulfonic acid sodium salt, initator dibenzoyl peroxide, Graphene concentrate adds in solvent dimethylacetylamide respectively, mix formation polymeric solution, the relative total monomer acrylonitrile of first monomers acrylonitrile, the mass fraction of acrylamide and metering system benzene sulfonic acid sodium salt is 85%, the relative total monomer acrylonitrile of second comonomer acrylamide, the mass fraction of acrylamide and metering system benzene sulfonic acid sodium salt is 13%, the relative total monomer acrylonitrile of Third monomer metering system benzene sulfonic acid sodium salt, the mass fraction of acrylamide and metering system benzene sulfonic acid sodium salt is 2%, polyase 13 h under normal pressure 60 DEG C of temperature conditions, monomers acrylonitrile, acrylamide and metering system benzene sulfonic acid sodium salt conversion ratio are 75%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile, acrylamide and the mass concentration of metering system benzene sulfonic acid sodium salt in polymeric solution are 15%, initator dibenzoyl peroxide relative monomer acrylonitrile, the mass percent of acrylamide and metering system benzene sulfonic acid sodium salt is 0.8%, Graphene concentrate relative monomer acrylonitrile, the mass percent of acrylamide and metering system benzene sulfonic acid sodium salt is 10%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethylacetylamide containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be dimethylacetylamide containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 6.67% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Embodiment 12

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile, second comonomer methyl acrylate and Third monomer vinylpyridine, initator dilauroyl peroxide, Graphene concentrate adds in solvent sodium sulfocyanate respectively, mix formation polymeric solution, the mass fraction of the relative total monomer of the first monomer is 84%, the mass fraction of the relative total monomer of second comonomer is 15%, the mass fraction of the relative total monomer of Third monomer is 1%, 4h is polymerized under normal pressure 55 DEG C of temperature conditions, monomer conversion is 72%, obtain polyacrylonitrile spinning solution, the relative total monomer acrylonitrile of first monomers acrylonitrile, the mass fraction of methyl acrylate and vinylpyridine is 80%, the relative total monomer acrylonitrile of second comonomer, the mass fraction of methyl acrylate and vinylpyridine is 10%, the relative total monomer acrylonitrile of Third monomer, the mass fraction of methyl acrylate and vinylpyridine is 10%, monomers acrylonitrile, methyl acrylate and the vinylpyridine mass concentration in polymeric solution is 20%, initator dilauroyl peroxide relative monomer acrylonitrile, the mass percent of methyl acrylate and vinylpyridine is 1.0%, Graphene concentrate relative monomer acrylonitrile, the mass percent of methyl acrylate and vinylpyridine is 25%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be sodium sulfocyanate containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 13.9% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4.8W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is

2.5cN/dtex。

Embodiment 13

Then carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing is obtained by in-situ polymerization, the concrete steps of in-situ polymerization are: by the first monomers acrylonitrile, second comonomer methyl acrylate and Third monomer dimethylaminoethyl acrylate methyl are for amino ethyl ester, initator dilauroyl peroxide, Graphene concentrate adds in solvent sodium sulfocyanate respectively, mix formation polymeric solution, the relative total monomer acrylonitrile of first monomers acrylonitrile, methyl acrylate and dimethylaminoethyl acrylate methyl replace the mass fraction of amino ethyl ester to be 98%, the relative total monomer acrylonitrile of second comonomer methyl acrylate, methyl acrylate and dimethylaminoethyl acrylate methyl replace the mass fraction of amino ethyl ester to be 1%, Third monomer dimethylaminoethyl acrylate methyl is for the relative total monomer acrylonitrile of amino ethyl ester, methyl acrylate and dimethylaminoethyl acrylate methyl replace the mass fraction of amino ethyl ester to be 1%, 4h is polymerized under normal pressure 55 DEG C of temperature conditions, monomer conversion is 72%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile and the methyl acrylate mass concentration in polymeric solution is 20%, the mass percent of initator dilauroyl peroxide relative monomer acrylonitrile and methyl acrylate is 1.0%, the mass percent of Graphene concentrate relative monomer acrylonitrile and methyl acrylate is 25%, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology, be specially: spinning solution is extruded through spinning head and entered coagulating bath, spinning head extruded velocity 0.5m/min, draw ratio 5 times, and then enter pre-heating bath successively, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, temperature is 20 DEG C, pre-heating bath to be sodium sulfocyanate containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C, the water temperature of rinsing bowl is 50 DEG C, stretch bath is the water containing 2% dioctyl succinate disulfonate acid, temperature 95 DEG C, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying process, obtained high heat conduction polyacrylonitrile fibre, containing the superfine graphite alkene of 11.1% in this high heat conduction polyacrylonitrile fibre, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer, the thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 3.8W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, and fracture strength is 2.5cN/dtex.

Claims

1. the preparation method of one kind high heat conduction polyacrylonitrile fibre, it is characterized in that, carry out adding Graphene concentrate when polymerisation prepares polyacrylonitrile at acrylonitrile, obtained the polyacrylonitrile spinning solution of graphene-containing by in-situ polymerization, spinning solution obtains high heat conduction polyacrylonitrile fibre through wet spinning technology;

2. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterized in that, the concrete steps of in-situ polymerization are: monomer, initator, Graphene concentrate are added respectively in solvent, mix and make polymeric solution; Under normal pressure 50 ~ 70 DEG C of temperature conditions, be polymerized 2 ~ 5h, monomer conversion is 70 ~ 85%, obtains polyacrylonitrile spinning solution; Described monomer at least comprises the first monomer, and the first described monomer is acrylonitrile;

3. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 2, it is characterized in that, described monomer is except comprising the first monomer, also comprise second comonomer, described second comonomer is the one in acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate; The mass fraction of the relative total monomer of the first monomer is 80 ~ 99%, and the mass fraction of the relative total monomer of second comonomer is 1 ~ 20%.

4. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 3, it is characterized in that, described monomer comprises the first monomer, second comonomer and Third monomer, and described Third monomer is that itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, dimethylaminoethyl acrylate methyl are for the one in amino ethyl ester; The mass fraction of the relative total monomer of the first monomer is 80 ~ 98%, and the mass fraction of the relative total monomer of second comonomer is 1 ~ 17%, and the mass fraction of the relative total monomer of Third monomer is 1 ~ 3%.

5. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 2, it is characterized in that, described initator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate; Described solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate.

6. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterized in that, the mass fraction of described graphene powder in described graphene dispersing solution is 0.5 ~ 8%, the quality of described aqueous titanic acid ester is less than or equal to 2% of graphene powder quality, and in described Graphene concentrate, the mass fraction of Graphene is 30-70%;

Described aqueous titanic acid ester is Di(dioctylpyrophosphato) ethylene titanate, or the chelate solution of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine, or two (dioctylphyrophosphoric acid ester) oxyacetate titanate esters, or two (dioctyl diethanol) ethylenediamine titanate esters, or two (octyl phenol polyoxyethylene ether) phosphide;

The process of described dissolving is by churned mechanically mode, and rotating speed is 50 ~ 100 revs/min, and mixing time is 5 ~ 30 minutes, and temperature is 10 ~ 35 DEG C;

Described superfine graphite alkene powder is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 6 ~ 10 nanometers; In described Graphene concentrate, superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer;

Magnetic field intensity corresponding to described ultrasonic disperse magnetic field is 0.5 ~ 5T; The magnetic field intensity of described externally-applied magnetic field is 2-6T;

The ultrasonic frequency of described ultrasonic disperse is 20 ~ 30KHz, and power is 1-5 kilowatt, and the ultrasonic disperse time is 30 ~ 90 minutes, and it is 10 ~ 60 DEG C that temperature controls;

The parameter of described decompression distillation is: vacuum is-0.01MPa ~-0.1MPa, and vapo(u)rizing temperature is 50 ~ 80 DEG C, and distillation time is 10 ~ 30 minutes.

7. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterized in that, described wet spinning technology is: spinning solution is extruded through spinning head and entered coagulating bath, and then enter pre-heating bath, rinsing bowl and stretch bath successively, in drying machine, compacting by drying is carried out again after oiling, steam heat sizing is carried out through the curling gas steamer that enters again of crimping machine, steam pressure is 0.2 ~ 0.3MPa, shaping time 10 ~ 30 minutes, tow, again through oiling and compacting by drying process, obtains high heat conduction polyacrylonitrile fibre;

Described coagulating bath is the aqueous solution containing the corresponding solvent dimethylformamide of mass fraction 30 ~ 40%, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate, temperature 20 ~ 30 DEG C;

Described pre-heating bath is the sulfosalt surfactant aqueous solution containing the corresponding solvent dimethylformamide of mass fraction 5 ~ 10%, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium sulfocyanate and 2%, temperature 60 ~ 65 DEG C;

The water temperature of described rinsing bowl 50 ~ 65 DEG C;

Described stretch bath is the water containing 2% sulfosalt surfactant, temperature 95 ~ 98 DEG C;

Spinning head extruded velocity 0.5 ~ 1m/min, draw ratio 5 ~ 7 times;

8. the high heat conduction polyacrylonitrile fibre of one that preparation method obtains according to any one of above claim 1-7, is characterized in that: containing the superfine graphite alkene of 0.5 ~ 15% in described high heat conduction polyacrylonitrile fibre; The thermal conductivity factor of described high heat conduction polyacrylonitrile fibre is 1 ~ 5W/mk.

9. the high heat conduction polyacrylonitrile fibre of one according to claim 8, is characterized in that, the viscosity average molecular weigh of described polyacrylonitrile is 50,000 ~ 100,000; Described superfine graphite alkene is of a size of: long and be widely respectively 1 ~ 10 micron, and thickness is 1 ~ 6 nanometer.

10. the high heat conduction polyacrylonitrile fibre of one according to claim 8, is characterized in that, the filament number of described high heat conduction polyacrylonitrile fibre is 1.0 ~ 3.3dtex, and fracture strength is 2.5 ~ 6.5cN/dtex.