CN104846466B

CN104846466B - A kind of high heat conduction polyacrylonitrile fibre and preparation method thereof

Info

Publication number: CN104846466B
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: 2018-02-27
Anticipated expiration: 2035-04-09
Also published as: CN104846466A

Abstract

The present invention relates to a kind of high heat conduction polyacrylonitrile fibre and preparation method thereof, is especially to provide a kind of addition graphene concentrate when acrylonitrile carries out polymerisation so that graphene uniform is dispersed in polyacrylonitrile spinning solution and high heat conduction polyacrylonitrile fibre of wet spinning preparation and preparation method thereof is carried out to stoste.The present invention first by superfine graphite alkene in the aqueous solution of aqueous titanic acid ester by magnetic field, be ultrasonically treated, carry out distilling obtained graphene concentrate in magnetic field again, monomer, initiator and graphene concentrate are added separately to carry out heating polymerisation in solvent, polyacrylonitrile spinning solution is made after terminating in reaction, and finally carrying out wet spinning to spinning solution is made high heat conduction polyacrylonitrile fibre.Contain the superfine graphite alkene of dispersed specially treated mistake in the high heat conduction polyacrylonitrile fibre, treated graphene can be combined well with polyacrylonitrile, so as to greatly improve the heat conductivility 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, is related to a kind of high heat conduction polyacrylonitrile fibre and its preparation side Method, graphene uniform is made more particularly to a kind of will be added to through treated graphene concentrate during acrylonitrile polymerization Scattered polyacrylonitrile spinning solution, and carry out wet spinning operation with polyacrylonitrile spinning solution and high heat conduction polyacrylonitrile is made The preparation method of fiber.

Background technology

Polyacrylonitrile fibre is one of synthetic fibers four major varieties, its yield be only second in synthetic fibers polyester fiber and Fypro, global yield have reached 3,000,000 tons/year.Polyacrylonitrile fibre is a kind of excellent textile product raw material, Fiber is fast light, radioresistance, softness, warming, is described as " artificial wool ", is widely used in the spinning such as garment material, tarpaulin, curtain Knit field.But it is growing with people's living standards continue to improve and clothing design, warming has no longer been clothes Unitary request, people are to its comfort level, feature and security requirement more and more higher.Insulation garment can hinder when temperature is relatively low Only human heat outwards discharges, and so as to reach warming effect, but will lose its work in temperature higher summer, this clothes With, so, if a kind of clothes that heat can be promoted to discharge can be invented, it will effectively solve the problems, such as the clothes of hot weather, make People it is more comfortable face hot weather.

Another main application of polyacrylonitrile fibre is prepares carbon fiber, and carbon fiber is with its outstanding mechanical performance in military affairs And the every field of civilian industry obtains extensive use.From the civilian work such as space flight, aviation, automobile, electronics, machinery, chemical industry, light textile Industry is to sports equipment and leisure goods etc..The use approach of carbon fiber is mainly with compound for the increasing of main carbon fiber with other materials at present Strong composite can be for the industrial circles such as the military industry fields such as aircraft manufacturing, wind power generation blade, electromagnetic shielding except electricity The body such as material, artificial ligament substitute material and for manufacture rocket envelope, power ship, industrial robot, leaf springs of car and The sports fields such as drive shaft, baseball, so, carbon fiber is the infant industry material in typical high-tech area.Carbon fiber exists With other materials it is compound after, its outstanding physical property and chemical property can only some embody in the composite, For the more preferable carbon fibre composite of processability, the performance of carbon fiber is lifted from source becomes a kind of effective solution Method.

The A of patent of invention CN 103484966 describe a kind of preparation method of the polyacrylonitrile fibre with anti-flammability, should Invention is by adding fire retardant when preparing polyacrylonitrile fibre spinning solution and by special process processing final poly- third Alkene nitrile fiber has certain anti-flammability.The invention is first mixed polyacrylonitrile, acrylonitrile and phosphonium flame retardant again to mixed Compound such as is freezed, is irradiated, polymerize and washed at the operation, and last obtained spinning solution carries out spinning and obtains polypropylene flame redardant Nitrile fiber, this method technique is more complicated, and fire retardant does not pass through specially treated, and this just easily causes final fiber product Fibre strength declines to a great extent.

The content of the invention

The present invention relates to a kind of high heat conduction polyacrylonitrile fibre and preparation method thereof, is especially to provide one kind and enters in acrylonitrile Graphene concentrate is added during row polymerisation causes graphene uniform to be dispersed in polyacrylonitrile spinning solution and enter to stoste High heat conduction polyacrylonitrile fibre prepared by row wet spinning and preparation method thereof.The present invention is first by superfine graphite alkene in aqueous titanic acid In the aqueous solution of ester by magnetic field, be ultrasonically treated, then carry out in magnetic field distilling obtained graphene concentrate, by monomer, trigger Agent and graphene concentrate are added separately to carry out heating polymerisation in solvent, and polyacrylonitrile spinning is made after terminating in reaction Stoste, wet spinning finally is carried out to spinning solution high heat conduction polyacrylonitrile fibre is made.The high heat conduction polyacrylonitrile fibre In contain the superfine graphite alkene of dispersed specially treated mistake, treated graphene can tie well with polyacrylonitrile Close, so as to greatly improve the heat conductivility of polyacrylonitrile.

A kind of preparation method of high heat conduction polyacrylonitrile fibre of the present invention, carry out polymerisation in acrylonitrile and prepare poly- third Graphene concentrate is added during alkene nitrile, the polyacrylonitrile spinning solution of graphene-containing, spinning solution warp are made by in-situ polymerization Cross wet spinning technology and high heat conduction polyacrylonitrile fibre is made；

The preparation method of the graphene concentrate：First aqueous titanic acid ester is dissolved in water, then adds superfine graphite Alkene powder, ultrasonic disperse is carried out in magnetic field, that is, obtains graphene dispersing solution；Then under additional magnetic fields, by graphene Dispersion liquid is distilled or is evaporated under reduced pressure, that is, obtains graphene concentrate.

As preferable technical scheme：

A kind of preparation method of high heat conduction polyacrylonitrile fibre as described above, in-situ polymerization concretely comprise the following steps：Will be single Body, initiator, graphene concentrate are separately added into solvent, well mixed that polymeric solution is made；In 50~70 DEG C of temperature of normal pressure Under the conditions of polymerize 2~5h, monomer conversion be 70~85%, obtain polyacrylonitrile spinning solution；Described monomer comprises at least First monomer, the first described monomer are acrylonitrile；

Mass concentration of the monomer in polymeric solution is 10~35%, and the mass percent of initiator relative monomer is 0.5 ~1.5%, the mass percent of graphene concentrate relative monomer is 0.7~33%.

A kind of preparation method of high heat conduction polyacrylonitrile fibre as described above, described monomer, which removes, includes the first monomer Outside, in addition to second comonomer, described second comonomer are acrylamide, methyl acrylate, methyl methacrylate, metering system One kind in nitrile, vinylacetate；First single phase is 80~99% to the mass fraction of total monomer, and second comonomer is relatively total single The mass fraction of body is 1~20%.

A kind of preparation method of high heat conduction polyacrylonitrile fibre as described above, described monomer include the first monomer, the Two monomers and Third monomer, described Third monomer are itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene Sodium sulfonate, vinylpyridine, dimethylaminoethyl acrylate methyl replace one kind in amino ethyl ester；Quality point of first single phase to total monomer Number is 80~98%, and second comonomer is 1~17% with respect to the mass fraction of total monomer, quality point of the Third monomer with respect to total monomer Number is 1~3%.

A kind of preparation method of high heat conduction polyacrylonitrile fibre as described above, described initiator is the isobutyl of azo two One kind in nitrile, ABVN, dibenzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate；It is described Solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethyl acetamide or sodium sulfocyanate.

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

Described aqueous titanic acid ester is Di(dioctylpyrophosphato) ethylene titanate, or double (two octyloxy Jiao's phosphorus Perester radical) ethylene titanate esters and triethanolamine chelate solution, or double (dioctylphyrophosphoric acid ester) oxyacetate titanate esters, or Double (dioctyl diethanol) ethylenediamine titanate esters, or two (octyl phenol APEO) phosphides, aqueous titanic acid ester contains can The lower alkyloxy of hydrolysis chemical reaction can occur with the double bond of graphene so that titanate esters can fully be combined with graphene, Play a part of surface modification so that superfine graphite alkene has higher activity.；

The process of the dissolving is by churned mechanically mode, and rotating speed is 50~100 revs/min, mixing time is 5~ 30 minutes, temperature was 10~35 DEG C, and aqueous titanic acid ester can be miscible with water, and we accelerate titanate esters dissolving speed by stirring at low speed Degree, significantly shortens dissolution time；

The size of the superfine graphite alkene powder is：Long and wide respectively 1~10 micron, thickness is 6~10 nanometers；It is described The size of superfine graphite alkene is in graphene concentrate：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer.Graphene Granularity it is smaller, corresponding specific surface area is bigger, and the graphene of small particle size is more beneficial for playing graphene outstanding Mechanical performance and other physical properties, and the usage amount of graphene can also be reduced when in use；

Magnetic field intensity corresponding to the ultrasonic disperse magnetic field is 0.5~5T；The magnetic field intensity of the externally-applied magnetic field be 2~ 6T, black alkene material has special structural form, and in magnetic field, the graphene in graphene dispersing solution can produce orderly orientation Arrangement, in concentration process, because the content of graphene gradually rises, the viscosity of graphene concentrate can become larger, because This, 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, and power is 1~5 kilowatt, and the ultrasonic disperse time is 30 ~90 minutes, temperature control was 10~60 DEG C, and ultrasonic disperse has good effect to scattered in dispersion liquid of graphene, Can sufficiently cause graphenic surface modified by aqueous titanic acid ester, in addition, graphene by magnetic fields in graphene dispersion After being aligned in liquid so as to reach a poised state, because the high-frequency of ultrasound acts on, so that this poised state It is broken, passes through continuous mechanical function so that the distance between graphene sheet layer increases, so as to have the function that stripping；

The distillation refers to cause graphene concentration raising in graphene dispersing solution by heating moisture evaporation Process, vapo(u)rizing temperature are 80~100 DEG C, and distillation time is 10~60 minutes；

The parameter of the vacuum distillation is：Vacuum is -0.01MPa~-0.1MPa, and vapo(u)rizing temperature is 50~80 DEG C, is steamed The time is evaporated for 10~30 minutes, by distilling or being evaporated under reduced pressure so that the moisture evaporation in graphene dispersing solution is separated and caused Graphene content increases substantially, and moisture content is greatly decreased, effectively improve due to moisture content is excessive and caused by produce and process and ask Topic；

A kind of preparation method of high heat conduction polyacrylonitrile fibre as described above, the wet spinning technology are：Spinning is former Liquid extrudes into coagulating bath through spinning head, then sequentially enters pre- heating bath, rinsing bowl and stretch bath again, then in drying after oiling Densification is dried in machine, through crimping machine curling enter back into gas steamer carry out steam thermal finalization, steam pressure be 0.2~ Through oiling and compacting by drying processing, it is fine that high heat conduction polyacrylonitrile is made again in 0.3MPa, shaping time 10~30 minutes, tow Dimension；

The coagulating bath is containing corresponding solvent dimethylformamide, dimethyl sulfoxide (DMSO), dimethyl acetamide or thiocyanic acid The aqueous solution of sodium mass fraction 30~40%, 20~30 DEG C of temperature, in coagulating bath contain with identical solvent in polymerization technique, make Obtaining fibre bundle can faster be molded；

The pre- heating bath is to contain 5~10% corresponding solvent dimethylformamide of mass fraction, dimethyl sulfoxide (DMSO), dimethyl Acetamide or sodium sulfocyanate and the 2% sulfosalt surfactant aqueous solution, 60~65 DEG C of temperature, surfactant can be effective Improve the surface of fibre bundle；

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

The stretch bath is the water containing 2% sulfosalt surfactant, 95~98 DEG C of temperature, high temperature and surfactant It can cause fiber that there is more preferable ductility；

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

Described sulfosalt surfactant is dioctyl succinate disulfonate acid, neopelex or glycocholic acid Sodium.

The present invention also proposes to gather by a kind of high heat conduction polyacrylonitrile fibre, the high heat conduction made from method made above Contain 0.5~15% superfine graphite alkene in Dralon；The thermal conductivity factor of the high heat conduction polyacrylonitrile fibre be 1~ 5W/m·k。

As preferable technical scheme：

A kind of high heat conduction polyacrylonitrile fibre of the present invention, the viscosity average molecular weigh of the polyacrylonitrile is 50,000~100,000；Institute The size for stating superfine graphite alkene is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；The high heat conduction polyacrylonitrile The filament number of fiber is 1.0~3.3dtex, and fracture strength is 2.5~6.5cN/dtex.

Beneficial effect：

A kind of preparation method of high heat conduction polyacrylonitrile fibre of the present invention, design is unique, and step is easy, positive effect.

The high heat conduction polyacrylonitrile fibre of the present invention, fiber thermal conductivity is good, and mechanical strength is good, and graphene dispersion is uniform, and The graphene film number of plies is small, and addition is few.Graphene passes through the surface treatment of aqueous titanic acid ester, the active group that graphenic surface introduces Group can be good at improving the compatibility and adhesion of graphene and polyacrylonitrile, and so as to be made, graphene uniform is scattered to be incorporated in High heat conduction polyacrylonitrile fibre in polyacrylonitrile fibre.Multi-layer graphene in the solution by magnetic field and ultrasound effect, Sandwich construction can be destroyed the few layer of production or single-layer graphene, and it is outstanding that few layer or single-layer graphene can preferably play graphene Physical characteristic or chemical characteristic, also, multi-layer graphene is made few layer or single-layer graphene by processing and means that our energy Lifting of addition of the graphene in polyacrylonitrile fibre without influenceing polyacrylonitrile fibre heat conductivility is enough greatly decreased.It is high The preparation of heat conduction polyacrylonitrile fibre, solve the problems, such as that some polyacrylonitrile fibres use field poor radiation, it is effective to expand Big polyacrylonitrile fibre uses field.

The present invention solves the problems, such as that polyacrylonitrile fibre uses field poor radiation some, by gathering in polyacrylonitrile The graphene crossed by aqueous titanic acid ester moditied processing is directly added during conjunction so that graphene uniform is dispersed in polyacrylonitrile fibre So as to reaching the good improvement of polyacrylonitrile fibre heat conductivility in dimension.By using special method to graphene at Reason, can effectively play the thermal conductivity of high heat conduction polyacrylonitrile fibre and the usage amount of graphene is greatly decreased；By this High heat conduction polyacrylonitrile fibre made from method, the decline of polyacrylonitrile fibre mechanical performance is avoided, it is not only obtained poly- Dralon has good thermal conductivity, and using the carbon fiber obtained by this high heat conduction polyacrylonitrile fibre, it is led It is hot also to have significant improvement.By solving these technical problems, polyacrylonitrile fibre uses field more comprehensive, The application method of graphene is more perfect, and therefore, this invention has great use value.

Embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.

Embodiment 1

A kind of preparation method of high heat conduction polyacrylonitrile fibre, graphene concentrate is made first, concretely comprises the following steps：

First aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate solution is dissolved in water, the mistake of dissolving Journey is by churned mechanically mode, and rotating speed is 50 revs/min, and mixing time is 5 minutes, and temperature is 10 DEG C, then adds length With it is wide be respectively 1~200 micron, thickness is 6~10 nanometers of graphene powder, double (the two octyloxy pyrophosphoric acids of aqueous titanic acid ester Ester group) ethylene titanate esters quality be Graphene powder weight 2%, magnetic field intensity be 0.5T magnetic field in carry out ultrasound point Dissipate, the ultrasonic frequency of ultrasonic disperse is 20KHz, and power is 1 kilowatt, and the ultrasonic disperse time is 30 minutes, temperature control 10 DEG C, that is, graphene dispersing solution is obtained, mass fraction of the graphene powder in graphene dispersing solution is 0.5%；Then in magnetic field Under the externally-applied magnetic field effect that intensity is 2T, graphene dispersing solution is distilled or is evaporated under reduced pressure, distillation refers to make by heating Obtain moisture evaporation and cause the process that graphene concentration improves in graphene dispersing solution, vapo(u)rizing temperature is 80 DEG C, and distillation time is 10 minutes；The parameter of vacuum distillation is：Vacuum is -0.01MPaMPa, and vapo(u)rizing temperature is 50 DEG C, and distillation time is 10 minutes, 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 the size of graphene is in graphene concentrate：It is long and wide respectively 1~200 micron, it is thick Spend for 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：Monomers acrylonitrile, initiator azo two is different Butyronitrile, graphene concentrate are separately added into solvent dimethylformamide, well mixed to form polymeric solution；In 50 DEG C of temperature of normal pressure It polymerize 2h under the conditions of degree, monomers acrylonitrile conversion ratio is 70%, obtains polyacrylonitrile spinning solution, and monomers acrylonitrile is molten in polymerization Mass concentration in liquid is 10%, and the mass percent of initiator azodiisobutyronitrile relative monomer acrylonitrile is 0.5%, graphite The mass percent of alkene concentrate relative monomer acrylonitrile is 2%, and spinning solution is made high heat conduction by wet spinning technology and gathered Dralon, it is specially：Spinning solution extrudes into coagulating bath, spinning head extruded velocity 0.5m/min, stretching through spinning head 5 times of multiple, then sequentially enters pre- heating bath, rinsing bowl and stretch bath again, and coagulating bath is the dimethyl containing mass fraction 30% The aqueous solution of formamide, temperature are 20 DEG C；Pre- heating bath is the dimethyl formamide solution containing mass fraction 5% and quality point Count the dioctyl succinate disulfonate acid solution for 2%, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is pungent containing 2% 2 The water of base sodium sulfosuccinate, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, through crimping machine curling again Steam thermal finalization is carried out into gas steamer, steam pressure 0.2MPa, shaping time 10 minutes, tow is again through oiling with drying cause Densification process, high heat conduction polyacrylonitrile fibre is made, contains 0.85% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre； Superfine graphite alkene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；High heat conduction polyacrylonitrile fibre is led Hot coefficient is 1W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 2

First by the chelate (model of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine 311W) solution is dissolved in water, and the process of dissolving is by churned mechanically mode, and rotating speed is 100 revs/min, mixing time For 30 minutes, temperature was 35 DEG C, and it is respectively 1~200 micron that then addition is long and wide, and thickness is 6~10 nanometers of Graphene powder The quality of the chelate solution of body, aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is stone The 1.5% of black alkene powder quality, ultrasonic disperse is carried out in the magnetic field that magnetic field intensity is 5T, the ultrasonic frequency of ultrasonic disperse is 30KHz, power are 5 kilowatts, and the ultrasonic disperse time is 90 minutes, and temperature control is 60 DEG C, that is, obtains graphene dispersing solution, graphite Mass fraction of the alkene powder in graphene dispersing solution is 8%；Then under the externally-applied magnetic field effect that magnetic field intensity is 6T, by stone Black alkene dispersion liquid is distilled or is evaporated under reduced pressure, and distillation refers to cause in graphene dispersing solution by heating moisture evaporation The process that graphene concentration improves, vapo(u)rizing temperature are 100 DEG C, and distillation time is 60 minutes；The parameter of vacuum distillation is：Vacuum For -0.1MPa, vapo(u)rizing temperature is 80 DEG C, and distillation time is 30 minutes, that is, obtains graphene concentrate, its be graphene powder, The uniform sizing material of water and aqueous titanic acid ester composition, the mass fraction of graphene is 70% in graphene concentrate, graphene concentration The size of graphene is in liquid：Long and wide respectively 1~200 micron, thickness is 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：Monomers acrylonitrile, initiator azo two is different Heptonitrile, graphene concentrate are separately added into solvent dimethyl sulfoxide (DMSO), well mixed to form polymeric solution；In 70 DEG C of temperature of normal pressure Under the conditions of polymerize 5h, monomers acrylonitrile conversion ratio is 85%, obtains polyacrylonitrile spinning solution, monomers acrylonitrile is in polymeric solution In mass concentration be 35%, the mass percent of initiator ABVN relative monomer acrylonitrile is 1.5%, graphene The mass percent of concentrate relative monomer acrylonitrile is 15%, and high heat conduction poly- third is made by wet spinning technology in spinning solution Alkene nitrile fiber, it is specially：Spinning solution extrudes into coagulating bath, spinning head extruded velocity 0.5m/min, stretching times through spinning head 5 times of number, then sequentially enters pre- heating bath, rinsing bowl and stretch bath again, and coagulating bath is sub- for the dimethyl containing mass fraction 30% The aqueous solution of sulfone, temperature are 20 DEG C；Pre- heating bath is the dimethyl sulphoxide solution containing mass fraction 5% and mass fraction is 2% dioctyl succinate disulfonate acid solution, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is containing 2% dioctyl amber The water of amber disulfonate acid, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, is entered back into through crimping machine curling Gas steamer carries out steam thermal finalization, and steam pressure 0.2MPa, shaping time 10 minutes, tow is again through oiling and compacting by drying Processing, high heat conduction polyacrylonitrile fibre is made, contains 14.9% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；It is ultra-fine Graphene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；The heat conduction system of high heat conduction polyacrylonitrile fibre Number is 5W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 3

First double (dioctylphyrophosphoric acid ester) the oxyacetate titanate esters of aqueous titanic acid ester are dissolved in water, the process of dissolving is By churned mechanically mode, rotating speed is 80 revs/min, and mixing time is 20 minutes, and temperature is 30 DEG C, is then added long and wide Respectively 1~200 micron, thickness is 6~10 nanometers of graphene powder, double (dioctylphyrophosphoric acid ester) the hydroxyl second of aqueous titanic acid ester The quality of acid esters titanate esters is the 1.5% of Graphene powder weight, carries out ultrasonic disperse in the magnetic field that magnetic field intensity is 2T, surpasses The scattered ultrasonic frequency of sound is 10KHz, and power is 3 kilowatts, and the ultrasonic disperse time is 50 minutes, and temperature control is 20 DEG C, i.e., Graphene dispersing solution is obtained, mass fraction of the graphene powder in graphene dispersing solution is 6%；Then it is 5T in magnetic field intensity Externally-applied magnetic field effect under, graphene dispersing solution is distilled or is evaporated under reduced pressure, distillation refer to by heat moisture steaming Send out and cause the process that graphene concentration improves in graphene dispersing solution, vapo(u)rizing temperature is 90 DEG C, and distillation time is 30 minutes；Subtract Pressure distillation parameter be：Vacuum is -0.05MPa, and vapo(u)rizing temperature is 60 DEG C, and distillation time is 15 minutes, that is, obtains graphene Concentrate, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, the quality of graphene in graphene concentrate Fraction is 50%, and the size of graphene is in graphene concentrate：Long and wide respectively 1~200 micron, thickness is received for 1~6 Rice.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Acrylamide, initiator dibenzoyl peroxide, graphene concentrate are separately added into solvent dimethyl acetamide, are well mixed Polymeric solution is formed, the first monomers acrylonitrile is 80% with respect to the mass fraction of total monomer acrylonitrile and acrylamide, and second is single Body acrylamide is 20% with respect to the mass fraction of total monomer；The polyase 13 h under 60 DEG C of temperature conditionss of normal pressure, monomers acrylonitrile and Acrylamide conversion ratio is 75%, obtains polyacrylonitrile spinning solution, monomers acrylonitrile and acrylamide are in polymeric solution Mass concentration is 15%, and the mass percent of initiator dibenzoyl peroxide relative monomer acrylonitrile and acrylamide is 0.8%, the mass percent of graphene concentrate relative monomer is 10%, and spinning solution is made height by wet spinning technology and led Hot polymerization Dralon, it is specially：

Spinning solution extrudes into coagulating bath through spinning head, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, so Sequentially enter pre- heating bath, rinsing bowl and stretch bath again afterwards, coagulating bath is the water of the dimethyl acetamide containing mass fraction 30% Solution, temperature are 20 DEG C；Pre- heating bath is the dimethylacetamide solution containing mass fraction 5% and mass fraction is 2% Dioctyl succinate disulfonate acid solution, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is containing 2% dioctyl succinate acid The water of sodium sulfonate, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, entering back into gas through crimping machine curling steams Pot carry out steam thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, tow again through oil with compacting by drying Reason, high heat conduction polyacrylonitrile fibre is made, contains 6.67% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；Ultra-fine stone Black alkene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre For 2.5W/mk, the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 4

First double (dioctyl diethanol) the ethylenediamine titanate esters of aqueous titanic acid ester are dissolved in water, the process of dissolving is to pass through Churned mechanically mode, rotating speed are 60 revs/min, and mixing time is 30 minutes, and temperature is 10 DEG C, then add long and wide difference For 1~200 micron, thickness is 6~10 nanometers of graphene powder, double (dioctyl diethanol) the ethylenediamine metatitanic acids of aqueous titanic acid ester The quality of ester is the 1.8% of Graphene powder weight, and ultrasonic disperse, ultrasonic disperse are carried out in the magnetic field that magnetic field intensity is 0.9T Ultrasonic frequency be 20KHz, power is 2 kilowatts, and the ultrasonic disperse time is 50 minutes, and temperature control is 20 DEG C, that is, obtains stone Black alkene dispersion liquid, mass fraction of the graphene powder in graphene dispersing solution are 2%；Then it is the additional of 3T in magnetic field intensity Under magnetic fields, graphene dispersing solution is distilled or is evaporated under reduced pressure, distillation refers to make by heating moisture evaporation The process that graphene concentration improves in graphene dispersing solution is obtained, vapo(u)rizing temperature is 80 DEG C, and distillation time is 60 minutes；It is evaporated under reduced pressure Parameter be：Vacuum is -0.1MPa, and vapo(u)rizing temperature is 50 DEG C, and distillation time is 10 minutes, that is, obtains graphene concentrate, It is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, and the mass fraction of graphene is in graphene concentrate 40%, the size of graphene is in graphene concentrate：Long and wide respectively 1~200 micron, thickness is 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Methyl acrylate, initiator dilauroyl peroxide, graphene concentrate are separately added into solvent sodium sulfocyanate, are well mixed and are formed Polymeric solution, the first single phase are 99% to the mass fraction of total monomer, and second comonomer is with respect to the mass fraction of total monomer 1%；It polymerize 4h under 55 DEG C of temperature conditionss of normal pressure, monomer conversion 72%, obtains polyacrylonitrile spinning solution, monomer propylene The mass concentration of nitrile and methyl acrylate in polymeric solution be 20%, initiator dilauroyl peroxide relative monomer acrylonitrile and The mass percent of methyl acrylate is 1.0%, the quality hundred of graphene concentrate relative monomer acrylonitrile and methyl acrylate Fraction is 25%, and high heat conduction polyacrylonitrile fibre is made by wet spinning technology in spinning solution, is specially：Spinning solution is through spray Silk head extrudes into coagulating bath, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enters pre- heating bath, water again Washing trough and stretch bath, coagulating bath are the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, and temperature is 20 DEG C；Pre- heating bath be containing Sodium sulfocyanate and the mass fraction for having mass fraction 5% are 2% dioctyl succinate disulfonate acid solution, temperature 60 C；Water The water temperature of washing trough is 50 DEG C；Stretch bath is the water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature；Again dry after oiling Densification is dried in dry machine, is crimped through crimping machine and enters back into the progress steam thermal finalization of gas steamer, steam pressure 0.2MPa, Again through oiling and compacting by drying processing, high heat conduction polyacrylonitrile fibre is made, the high heat conduction is gathered in shaping time 10 minutes, tow Contain 13.9% superfine graphite alkene in Dralon；Superfine graphite alkene size is：It is long and wide respectively 1~10 micron, it is thick Spend for 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4.5W/mk, the monofilament of high heat conduction polyacrylonitrile fibre Fiber number is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 5

First aqueous titanic acid ester two (octyl phenol APEO) phosphide is dissolved in water, the process of dissolving is to pass through Churned mechanically mode, rotating speed are 100 revs/min, and mixing time is 5 minutes, and temperature is 25 DEG C, then add long and wide difference For 1~200 micron, thickness is 6~10 nanometers of graphene powder, aqueous titanic acid ester two (octyl phenol APEO) phosphorus The quality of ester is the 2% of Graphene powder weight, and ultrasonic disperse is carried out in the magnetic field that magnetic field intensity is 0.8T, ultrasonic disperse Ultrasonic frequency is 25KHz, and power is 3 kilowatts, and the ultrasonic disperse time is 60 minutes, and temperature control is 30 DEG C, that is, obtains graphite Alkene dispersion liquid, mass fraction of the graphene powder in the graphene dispersing solution are 8%；Then it is the outer of 6T in magnetic field intensity Add under magnetic fields, graphene dispersing solution distilled or is evaporated under reduced pressure, distillation refer to by heat moisture evaporation and So that the process that graphene concentration improves in graphene dispersing solution, vapo(u)rizing temperature is 90 DEG C, and distillation time is 60 minutes；Decompression is steamed The parameter evaporated is：Vacuum is -0.01MPa, and vapo(u)rizing temperature is 50 DEG C, and distillation time is 10 minutes, that is, obtains graphene concentration Liquid, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, the mass fraction of graphene in graphene concentrate For 30%, the size of graphene is in graphene concentrate：Long and wide respectively 1~200 micron, thickness is 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Methyl methacrylate, initiator di-isopropyl peroxydicarbonate, graphene concentrate are separately added into solvent dimethyl formyl Well mixed to form polymeric solution in amine, the first single phase is 90% to the mass fraction of total monomer, and second comonomer is relatively total single The mass fraction of body is 10%；It polymerize 5h, monomers acrylonitrile and methyl methacrylate conversion under 60 DEG C of temperature conditionss of normal pressure Rate is 70%, obtains polyacrylonitrile spinning solution, and the quality of monomers acrylonitrile and methyl methacrylate in polymeric solution is dense Spend for 25%, the mass percent of initiator di-isopropyl peroxydicarbonate relative monomer acrylonitrile and methyl methacrylate For 1.2%, the mass percent of graphene concentrate relative monomer acrylonitrile and methyl methacrylate is 12%, spinning solution High heat conduction polyacrylonitrile fibre is made by wet spinning technology, is specially：Spinning solution extrudes into coagulating bath through spinning head, Spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enters pre- heating bath, rinsing bowl and stretch bath, coagulating bath again For the aqueous solution of the dimethylformamide containing mass fraction 30%, temperature is 20 DEG C；Pre- heating bath is to contain mass fraction 5% Dimethyl formamide solution and the dioctyl succinate disulfonate acid solution that mass fraction is 2%, temperature 60 C；The water of rinsing bowl Temperature is 50 DEG C；Stretch bath is the water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature；Enter again after oiling in drying machine Row compacting by drying, enter back into gas steamer through crimping machine curling and carry out steam thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, again through oiling and compacting by drying processing, high heat conduction polyacrylonitrile fibre was made, the high heat conduction polyacrylonitrile is fine in tow Contain 5.14% superfine graphite alkene in dimension；Superfine graphite alkene size is：Long and wide respectively 1~10 micron, 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, fracture strength 2.5cN/dtex.

Embodiment 6

First double (dioctyl diethanol) the ethylenediamine titanate esters of aqueous titanic acid ester are dissolved in water, the process of dissolving is to pass through Churned mechanically mode, rotating speed are 50 revs/min, and mixing time is 5 minutes, and temperature is 35 DEG C, then add long and wide difference For 1~200 micron, thickness is 6~10 nanometers of graphene powder, double (dioctyl diethanol) the ethylenediamine metatitanic acids of aqueous titanic acid ester The quality of ester is the 0.8% of Graphene powder weight, and ultrasonic disperse, ultrasonic disperse are carried out in the magnetic field that magnetic field intensity is 0.9T Ultrasonic frequency be 30KHz, power is 5 kilowatts, and the ultrasonic disperse time is 90 minutes, and temperature control is 10 DEG C, that is, obtains stone Black alkene dispersion liquid, mass fraction of the graphene powder in the graphene dispersing solution are 0.5%；Then it is 2T in magnetic field intensity Externally-applied magnetic field effect under, graphene dispersing solution is distilled or is evaporated under reduced pressure, distillation refer to by heat moisture steaming Send out and cause the process that graphene concentration improves in graphene dispersing solution, vapo(u)rizing temperature is 80 DEG C, and distillation time is 30 minutes；Subtract Pressure distillation parameter be：Vacuum is -0.09MPa, and vapo(u)rizing temperature is 60 DEG C, and distillation time is 30 minutes, that is, obtains graphene Concentrate, it is the uniform sizing material of graphene powder, water and aqueous titanic acid ester composition, the quality of graphene in graphene concentrate Fraction is 50%, and the size of graphene is in graphene concentrate：Long and wide respectively 1~200 micron, thickness is received for 1~6 Rice.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Methacrylonitrile, initiator azodiisobutyronitrile, graphene concentrate are separately added into solvent dimethyl sulfoxide (DMSO), are well mixed shape Into polymeric solution, the first single phase is 85% to the mass fraction of total monomer, and second comonomer is with respect to the mass fraction of total monomer 15%.；It polymerize 5h under 70 DEG C of temperature conditionss of normal pressure, monomers acrylonitrile and methacrylonitrile conversion ratio are 80%, obtain poly- third Alkene nitrile spinning solution, the mass concentration of monomers acrylonitrile and methacrylonitrile in polymeric solution are 22%, initiator azo two The mass percent of isobutyronitrile relative monomer acrylonitrile and methacrylonitrile is 1.2%, graphene concentrate relative monomer propylene The mass percent of nitrile and methacrylonitrile is 10%, and high heat conduction polyacrylonitrile fibre is made by wet spinning technology in spinning solution Dimension, it is specially：Spinning solution extrudes into coagulating bath through spinning head, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, Then pre- heating bath, rinsing bowl and stretch bath are sequentially entered again, and coagulating bath is the water of the dimethyl sulfoxide (DMSO) containing mass fraction 30% Solution, temperature are 20 DEG C；Pre- heating bath is the dioctyl that the dimethyl sulfoxide (DMSO) containing mass fraction 5% and mass fraction are 2% Sodium sulfosuccinate solution, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is containing 2% dioctyl succinate disulfonate acid Water, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, entering back into gas steamer through crimping machine curling is carried out Steam thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, tow through oiling and compacting by drying processing, are made again High heat conduction polyacrylonitrile fibre, contain 6.67% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；Superfine graphite alkene chi It is very little to be：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 2.2W/ Mk, the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 7

First by the chelate (model of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine 311W) solution is dissolved in water, and it by churned mechanically mode, rotating speed is 60 revs/min that the process of dissolving, which is, and mixing time is 30 minutes, temperature was 35 DEG C, and it is respectively 1~200 micron that then addition is long and wide, and thickness is 6~10 nanometers of graphene powder, The quality of the chelate solution of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is graphite The 1.5% of alkene powder quality, ultrasonic disperse is carried out in the magnetic field that magnetic field intensity is 4T, the ultrasonic frequency of ultrasonic disperse is 28KHz, power are 5 kilowatts, and the ultrasonic disperse time is 90 minutes, and temperature control is 60 DEG C, that is, obtains graphene dispersing solution, graphite Mass fraction of the alkene powder in graphene dispersing solution is 8%；Then under the externally-applied magnetic field effect that magnetic field intensity is 5T, by stone Black alkene dispersion liquid is distilled or is evaporated under reduced pressure, and distillation refers to cause in graphene dispersing solution by heating moisture evaporation The process that graphene concentration improves, vapo(u)rizing temperature are 100 DEG C, and distillation time is 60 minutes；The parameter of vacuum distillation is：Vacuum For -0.1MPa, vapo(u)rizing temperature is 80 DEG C, and distillation time is 30 minutes, that is, obtains graphene concentrate, its be graphene powder, The uniform sizing material of water and aqueous titanic acid ester composition, the mass fraction of graphene is 70% in graphene concentrate, graphene concentration The size of graphene is in liquid：Long and wide respectively 1~200 micron, thickness is 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Vinylacetate, initiator ABVN, graphene concentrate are separately added into solvent dimethyl acetamide, are well mixed Polymeric solution is formed, the first single phase is 99% to the mass fraction of total monomer, mass fraction of the second comonomer with respect to total monomer For 1%；It polymerize 4h under 65 DEG C of temperature conditionss of normal pressure, monomer conversion 80%, obtains polyacrylonitrile spinning solution, monomer third The mass concentration of alkene nitrile and vinylacetate in polymeric solution is 20%, initiator ABVN relative monomer acrylonitrile Mass percent with vinylacetate is 1.0%, the quality of graphene concentrate relative monomer acrylonitrile and vinylacetate Percentage is 12%, and high heat conduction polyacrylonitrile fibre is made by wet spinning technology in spinning solution, is specially：Spinning solution passes through Spinning head extrudes into coagulating bath, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enter again pre- heating bath, Rinsing bowl and stretch bath, coagulating bath are the aqueous solution of the dimethyl acetamide containing mass fraction 30%, and temperature is 20 DEG C；Preheating Bathe for the dimethylacetamide solution containing mass fraction 5% and mass fraction be 2% dioctyl succinate disulfonate acid it is molten Liquid, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is the water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature； Densification is dried in drying machine after oiling again, entering back into gas steamer through crimping machine curling carries out steam thermal finalization, steams Steam pressure is 0.2MPa, shaping time 10 minutes, and through oiling and compacting by drying is handled, high heat conduction polyacrylonitrile is made again in tow Fiber, contain 10.5% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；Superfine graphite alkene size is：Long and wide difference For 1~10 micron, thickness is 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 3.5W/mk, high heat conduction poly- third The filament number of alkene nitrile fiber is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 8

First by the chelate solution of aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine (model 311W) is dissolved in water, and the process of dissolving is by churned mechanically mode, and rotating speed is 80 revs/min, mixing time For 30 minutes, temperature was 35 DEG C, and it is respectively 1~200 micron that then addition is long and wide, and thickness is 6~10 nanometers of Graphene powder The quality of the chelate solution of body, aqueous titanic acid ester Di(dioctylpyrophosphato) ethylene titanate and triethanolamine is stone The 1.5% of black alkene powder quality, ultrasonic disperse is carried out in the magnetic field that magnetic field intensity is 3T, the ultrasonic frequency of ultrasonic disperse is 30KHz, power are 5 kilowatts, and the ultrasonic disperse time is 90 minutes, and temperature control is 60 DEG C, that is, obtains graphene dispersing solution, graphite Mass fraction of the alkene powder in graphene dispersing solution is 8%；Then under the externally-applied magnetic field effect that magnetic field intensity is 3T, by stone Black alkene dispersion liquid is distilled or is evaporated under reduced pressure, and distillation refers to cause in graphene dispersing solution by heating moisture evaporation The process that graphene concentration improves, vapo(u)rizing temperature are 100 DEG C, and distillation time is 60 minutes；The parameter of vacuum distillation is：Vacuum For -0.1MPa, vapo(u)rizing temperature is 80 DEG C, and distillation time is 30 minutes, that is, obtains graphene concentrate, its be graphene powder, The uniform sizing material of water and aqueous titanic acid ester composition, the mass fraction of graphene is 70% in graphene concentrate, graphene concentration The size of graphene is in liquid：Long and wide respectively 1~200 micron, thickness is 1~6 nanometer.

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile and second comonomer Acrylamide, Third monomer itaconic acid, initiator dilauroyl peroxide, graphene concentrate are separately added into solvent sodium sulfocyanate In, well mixed to form polymeric solution, the first single phase is 80% to the mass fraction of total monomer, and second comonomer is with respect to total monomer Mass fraction be 17%, Third monomer with respect to total monomer mass fraction be 3%；It polymerize under 60 DEG C of temperature conditionss of normal pressure 5h, monomer conversion 85% obtain polyacrylonitrile spinning solution, and monomers acrylonitrile, acrylamide and itaconic acid are molten in polymerization Mass concentration in liquid is 10~35%, and the mass percent of initiator relative monomer acrylonitrile, acrylamide and itaconic acid is 1.0%, the mass percent of graphene concentrate relative monomer acrylonitrile, acrylamide and itaconic acid is 10%, spinning solution High heat conduction polyacrylonitrile fibre is made by wet spinning technology, is specially：Spinning solution extrudes into coagulating bath through spinning head, Spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enters pre- heating bath, rinsing bowl and stretch bath, coagulating bath again For the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, temperature is 20 DEG C；Pre- heating bath is the sulphur cyanogen containing mass fraction 5% Sour sodium and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Draw It is the water containing 2% dioctyl succinate disulfonate acid to stretch bath, 95 DEG C of temperature；Densification is dried in drying machine after oiling again Change, entering back into gas steamer through crimping machine curling carries out steam thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, silk Shu Zaijing oils and compacting by drying processing, and high heat conduction polyacrylonitrile fibre is made, contains in the high heat conduction polyacrylonitrile fibre 8.24% superfine graphite alkene；Superfine graphite alkene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；Height is led The thermal conductivity factor of hot polymerization Dralon is 2.8W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, is broken Resistance to spalling is 2.5cN/dtex.

Embodiment 9

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile, second comonomer third E pioic acid methyl ester and Third monomer sodium allylsulfonate, initiator dilauroyl peroxide, graphene concentrate are separately added into solvent diformazan Well mixed to form polymeric solution in base formamide, the first single phase is 98% to the mass fraction of total monomer, second comonomer phase Mass fraction to total monomer is 1%, and Third monomer is 1% with respect to the mass fraction of total monomer；In 65 DEG C of temperature conditionss of normal pressure Lower polyase 13 h, monomers acrylonitrile, methyl acrylate and sodium allylsulfonate conversion ratio are 75%, obtain polyacrylonitrile spinning solution, The mass concentration of monomers acrylonitrile, methyl acrylate and sodium allylsulfonate in polymeric solution is 25%, initiator peroxidating ten The mass percent of two acyl relative monomer acrylonitrile, methyl acrylate and sodium allylsulfonate is 1.2%, and graphene concentrate is relative The mass percent of monomer is 15%, and high heat conduction polyacrylonitrile fibre is made by wet spinning technology in spinning solution, is specially： Spinning solution extrudes into coagulating bath through spinning head, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then again successively Into pre- heating bath, rinsing bowl and stretch bath, coagulating bath is the aqueous solution of the dimethylformamide containing mass fraction 30%, temperature For 20 DEG C；Pre- heating bath is the dioctyl succinate that the dimethyl formamide solution containing mass fraction 5% and mass fraction are 2% 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, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, entering back into gas steamer through crimping machine curling carries out steam Thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, tow are led through oiling with compacting by drying processing, obtained height again Hot polymerization Dralon, contain 14% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；Superfine graphite alkene size is：It is long With it is wide be respectively 1~10 micron, thickness be 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 4.7W/mk, high The filament number of heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength 2.5cN/dtex.

Embodiment 10

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile, second comonomer first Base acrylonitrile and Third monomer methylpropene sodium sulfonate, initiator dibenzoyl peroxide, graphene concentrate are separately added into molten Well mixed to form polymeric solution in agent dimethyl sulfoxide (DMSO), the first single phase is 88% to the mass fraction of total monomer, and second is single Body phase is 10% to the mass fraction of total monomer, and Third monomer is 2% with respect to the mass fraction of total monomer；In 70 DEG C of temperature of normal pressure Under the conditions of polymerize 2h, monomers acrylonitrile, methacrylonitrile and methylpropene sodium sulfonate conversion ratio are 72%, obtain polyacrylonitrile spinning Silk stock solution, the mass concentration of monomers acrylonitrile, methacrylonitrile and methylpropene sodium sulfonate in polymeric solution are 25%, are triggered The mass percent of agent dibenzoyl peroxide relative monomer acrylonitrile, methacrylonitrile and methylpropene sodium sulfonate is 1.0%, The mass percent of graphene concentrate relative monomer acrylonitrile, methacrylonitrile and methylpropene sodium sulfonate is 12%, spinning High heat conduction polyacrylonitrile fibre is made by wet spinning technology in stoste, is specially：Spinning solution extrudes into solidifying through spinning head Gu bath, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enters pre- heating bath, rinsing bowl and stretch bath again, Coagulating bath is the aqueous solution of the dimethyl sulfoxide (DMSO) containing mass fraction 30%, and temperature is 20 DEG C；Pre- heating bath is to contain mass fraction 5% dimethyl sulfoxide (DMSO) and mass fraction be 2% dioctyl succinate disulfonate acid solution, temperature 60 C；The water of rinsing bowl Temperature is 50 DEG C；Stretch bath is the water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature；Enter again after oiling in drying machine Row compacting by drying, enter back into gas steamer through crimping machine curling and carry out steam thermal finalization, steam pressure 0.2MPa, shaping time 10 minutes, again through oiling and compacting by drying processing, high heat conduction polyacrylonitrile fibre was made, the high heat conduction polyacrylonitrile is fine in tow Contain 11.7% superfine graphite alkene in dimension；Superfine graphite alkene size is：Long and wide respectively 1~10 micron, 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, fracture strength 2.5cN/dtex.

Embodiment 11

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile, second comonomer third Acrylamide and Third monomer metering system benzene sulfonic acid sodium salt, initiator dibenzoyl peroxide, graphene concentrate are separately added into molten In agent dimethyl acetamide, well mixed to form polymeric solution, the first monomers acrylonitrile is with respect to total monomer acrylonitrile, acrylamide Mass fraction with metering system benzene sulfonic acid sodium salt is 85%, and second comonomer acrylamide is with respect to total monomer acrylonitrile, acrylamide Be 13% with the mass fraction of metering system benzene sulfonic acid sodium salt, Third monomer metering system benzene sulfonic acid sodium salt with respect to total monomer acrylonitrile, The mass fraction of acrylamide and metering system benzene sulfonic acid sodium salt is 2%；The polyase 13 h under 60 DEG C of temperature conditionss of normal pressure, monomer propylene Nitrile, acrylamide and metering system benzene sulfonic acid sodium salt conversion ratio are 75%, obtain polyacrylonitrile spinning solution, monomers acrylonitrile, third The mass concentration of acrylamide and metering system benzene sulfonic acid sodium salt in polymeric solution is 15%, and initiator dibenzoyl peroxide is relative The mass percent of monomers acrylonitrile, acrylamide and metering system benzene sulfonic acid sodium salt is 0.8%, graphene concentrate relative monomer The mass percent of acrylonitrile, acrylamide and metering system benzene sulfonic acid sodium salt is 10%, and spinning solution passes through wet spinning technology High heat conduction polyacrylonitrile fibre is made, is specially：Spinning solution extrudes into coagulating bath, spinning head extruded velocity through spinning head Then 0.5m/min, 5 times of draw ratio sequentially enter pre- heating bath, rinsing bowl and stretch bath again, coagulating bath is to contain mass fraction The aqueous solution of 30% dimethyl acetamide, temperature are 20 DEG C；Pre- heating bath be the dimethyl acetamide containing mass fraction 5% with And the dioctyl succinate disulfonate acid solution that mass fraction is 2%, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath is Water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, through volume Bent machine curling enters back into gas steamer and carries out steam thermal finalization, and steam pressure 0.2MPa, shaping time 10 minutes, tow is again through upper Oil is handled with compacting by drying, and high heat conduction polyacrylonitrile fibre is made, contains 6.67% in the high heat conduction polyacrylonitrile fibre Superfine graphite alkene；Superfine graphite alkene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；High heat conduction polypropylene The thermal conductivity factor of nitrile fiber 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 in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile, second comonomer third E pioic acid methyl ester and Third monomer vinylpyridine, initiator dilauroyl peroxide, graphene concentrate are separately added into solvent sulphur cyanogen Well mixed to form polymeric solution in sour sodium, the first single phase is 84% to the mass fraction of total monomer, and second comonomer is relatively total The mass fraction of monomer is 15%, and Third monomer is 1% with respect to the mass fraction of total monomer；Gather under 55 DEG C of temperature conditionss of normal pressure 4h is closed, monomer conversion 72%, obtains polyacrylonitrile spinning solution, the first monomers acrylonitrile is with respect to total monomer acrylonitrile, third The mass fraction of e pioic acid methyl ester and vinylpyridine is 80%, and second comonomer is with respect to total monomer acrylonitrile, methyl acrylate and second The mass fraction of alkenyl pyridine is 10%, matter of the Third monomer with respect to total monomer acrylonitrile, methyl acrylate and vinylpyridine It is 10% to measure fraction, and the mass concentration of monomers acrylonitrile, methyl acrylate and vinylpyridine in polymeric solution is 20%, is drawn The mass percent for sending out agent dilauroyl peroxide relative monomer acrylonitrile, methyl acrylate and vinylpyridine is 1.0%, graphite The mass percent of alkene concentrate relative monomer acrylonitrile, methyl acrylate and vinylpyridine is 25%, and spinning solution passes through High heat conduction polyacrylonitrile fibre is made in wet spinning technology, is specially：Spinning solution extrudes into coagulating bath, spinneret through spinning head Then head extruded velocity 0.5m/min, 5 times of draw ratio sequentially enter pre- heating bath, rinsing bowl and stretch bath again, coagulating bath be containing There is the aqueous solution of the sodium sulfocyanate of mass fraction 30%, temperature is 20 DEG C；Pre- heating bath is the sodium sulfocyanate containing mass fraction 5% And the dioctyl succinate disulfonate acid solution that mass fraction is 2%, temperature 60 C；The water temperature of rinsing bowl is 50 DEG C；Stretch bath For the water containing 2% dioctyl succinate disulfonate acid, 95 DEG C of temperature；Densification is dried in drying machine after oiling again, passes through Crimping machine curling enters back into gas steamer and carries out steam thermal finalization, and steam pressure 0.2MPa, shaping time 10 minutes, tow passes through again Oil and compacting by drying processing, high heat conduction polyacrylonitrile fibre is made, contains 13.9% in the high heat conduction polyacrylonitrile fibre Superfine graphite alkene；Superfine graphite alkene size is：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；High heat conduction poly- third The thermal conductivity factor of alkene nitrile fiber is 4.8W/mk, and the filament number of high heat conduction polyacrylonitrile fibre is 1.0dtex, fracture strength For

2.5cN/dtex。

Embodiment 13

Then carry out adding graphene concentrate when polymerisation prepares polyacrylonitrile in acrylonitrile, by in-situ polymerization system The polyacrylonitrile spinning solution of graphene-containing is obtained, in-situ polymerization concretely comprises the following steps：By the first monomers acrylonitrile, second comonomer third E pioic acid methyl ester and Third monomer dimethylaminoethyl acrylate methyl are for amino ethyl ester, initiator dilauroyl peroxide, graphene concentrate point Jia Ru not be in solvent sodium sulfocyanate, well mixed to form polymeric solution, the first monomers acrylonitrile is with respect to total monomer acrylonitrile, propylene Sour methyl esters and dimethylaminoethyl acrylate methyl are 98% for the mass fraction of amino ethyl ester, and second comonomer methyl acrylate is with respect to total monomer Acrylonitrile, methyl acrylate and dimethylaminoethyl acrylate methyl are 1% for the mass fraction of amino ethyl ester, Third monomer methacrylic acid Dimethylamino ethyl ester replaces the mass fraction of amino ethyl ester with respect to total monomer acrylonitrile, methyl acrylate and dimethylaminoethyl acrylate methyl For 1%；It polymerize 4h under 55 DEG C of temperature conditionss of normal pressure, monomer conversion 72%, obtains polyacrylonitrile spinning solution, monomer third The mass concentration of alkene nitrile and methyl acrylate in polymeric solution is 20%, initiator dilauroyl peroxide relative monomer acrylonitrile Mass percent with methyl acrylate is 1.0%, the quality of graphene concentrate relative monomer acrylonitrile and methyl acrylate Percentage is 25%, and high heat conduction polyacrylonitrile fibre is made by wet spinning technology in spinning solution, is specially：Spinning solution passes through Spinning head extrudes into coagulating bath, spinning head extruded velocity 0.5m/min, 5 times of draw ratio, then sequentially enter again pre- heating bath, Rinsing bowl and stretch bath, coagulating bath are the aqueous solution of the sodium sulfocyanate containing mass fraction 30%, and temperature is 20 DEG C；Pre- heating bath is Sodium sulfocyanate and mass fraction containing mass fraction 5% 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, 95 DEG C of temperature；Again after oiling Densification is dried in drying machine, entering back into gas steamer through crimping machine curling carries out steam thermal finalization, and steam pressure is High heat conduction polyacrylonitrile fibre is made again through oiling and compacting by drying is handled in 0.2MPa, shaping time 10 minutes, tow, should Contain 11.1% superfine graphite alkene in high heat conduction polyacrylonitrile fibre；Superfine graphite alkene size is：It is long and wide by respectively 1~10 Micron, thickness are 1~6 nanometer；The thermal conductivity factor of high heat conduction polyacrylonitrile fibre is 3.8W/mk, and high heat conduction polyacrylonitrile is fine The filament number of dimension is 1.0dtex, fracture strength 2.5cN/dtex.

Claims

1. a kind of preparation method of high heat conduction polyacrylonitrile fibre, it is characterised in that it is poly- to carry out polymerisation preparation in acrylonitrile Graphene concentrate is added during acrylonitrile, the polyacrylonitrile spinning solution of graphene-containing, spinning solution are made by in-situ polymerization High heat conduction polyacrylonitrile fibre is made by wet spinning technology；

The preparation method of the graphene concentrate：First aqueous titanic acid ester is dissolved in water, then adds superfine graphite alkene powder Body, ultrasonic disperse is carried out in magnetic field, that is, obtains graphene dispersing solution；Then under additional magnetic fields, by graphene dispersion Liquid is distilled or is evaporated under reduced pressure, that is, obtains graphene concentrate；

Mass fraction of the graphene powder in the graphene dispersing solution is 0.5~8%, the matter of the aqueous titanic acid ester 2% of amount less than or equal to Graphene powder weight, the mass fraction of graphene is 30-70% in the graphene concentrate；

Described aqueous titanic acid ester is Di(dioctylpyrophosphato) ethylene titanate, or double (two octyloxy pyrophosphates Base) ethylene titanate esters and triethanolamine chelate solution, or double (dioctylphyrophosphoric acid ester) oxyacetate titanate esters, or double (dioctyl diethanol) ethylenediamine titanate esters, or two (octyl phenol APEO) phosphides；

The size of the superfine graphite alkene powder is：Long and wide respectively 1~10 micron, thickness is 6~10 nanometers；The graphite The size of superfine graphite alkene is in alkene concentrate：Long and wide respectively 1~10 micron, thickness is 1~6 nanometer；

It is described distillation refer to the process of by heat moisture evaporation and cause graphene dispersing solution in graphene concentration raising, Vapo(u)rizing temperature is 80~100 DEG C, and distillation time is 10~60 minutes；

The parameter of the vacuum distillation is：Vacuum is -0.01MPa~-0.1MPa, and vapo(u)rizing temperature is 50~80 DEG C, during distillation Between be 10~30 minutes.

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

The ultrasonic frequency of described ultrasonic disperse is 20~30KHz, and power is 1-5 kilowatts, and the ultrasonic disperse time is 30~90 Minute, temperature control is 10~60 DEG C.

A kind of 2. preparation method of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterised in that in-situ polymerization Concretely comprise the following steps：Monomer, initiator, graphene concentrate are separately added into solvent, it is well mixed that polymeric solution is made； It polymerize 2~5h under 50~70 DEG C of temperature conditionss of normal pressure, monomer conversion is 70~85%, obtains polyacrylonitrile spinning solution；Institute The monomer stated comprises at least the first monomer, and the first described monomer is acrylonitrile；

Mass concentration of the monomer in polymeric solution is 10~35%, the mass percent of initiator relative monomer for 0.5~ 1.5%, the mass percent of graphene concentrate relative monomer is 0.7~33%.

A kind of 3. preparation method of high heat conduction polyacrylonitrile fibre according to claim 2, it is characterised in that described list Body is in addition to including the first monomer, in addition to second comonomer, and described second comonomer is acrylamide, methyl acrylate, methyl-prop One kind in e pioic acid methyl ester, methacrylonitrile, vinylacetate；First single phase to the mass fraction of total monomer for 80~ 99%, second comonomer is 1~20% with respect to the mass fraction of total monomer.

A kind of 4. preparation method of high heat conduction polyacrylonitrile fibre according to claim 3, it is characterised in that described list Body includes the first monomer, second comonomer and Third monomer, and described Third monomer is itaconic acid, sodium allylsulfonate, metering system Sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, dimethylaminoethyl acrylate methyl replace one kind in amino ethyl ester；First monomer Mass fraction with respect to total monomer is 80~98%, and second comonomer is 1~17% with respect to the mass fraction of total monomer, Third monomer Mass fraction with respect to total monomer is 1~3%.

5. the preparation method of a kind of high heat conduction polyacrylonitrile fibre according to claim 2, it is characterised in that described draws Hair agent is that azodiisobutyronitrile, ABVN, dibenzoyl peroxide, dilauroyl peroxide, dicetyl peroxydicarbonate two are different One kind in propyl ester；The solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethyl acetamide or sodium sulfocyanate.

A kind of 6. preparation method of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterised in that the dissolving Process be by churned mechanically mode, rotating speed is 50~100 revs/min, and mixing time is 5~30 minutes, temperature 10 ~35 DEG C；

A kind of 7. preparation method of high heat conduction polyacrylonitrile fibre according to claim 1, it is characterised in that the wet method Spinning technique is：Spinning solution extrudes into coagulating bath through spinning head, then sequentially enters pre- heating bath, rinsing bowl and stretching again Bath, then densification is dried in drying machine after oiling, entering back into gas steamer through crimping machine curling carries out steam thermal finalization, Steam pressure is 0.2~0.3MPa, shaping time 10~30 minutes, and through oiling and compacting by drying is handled, height is made again in tow Heat conduction polyacrylonitrile fibre；

The coagulating bath is to contain 30~40% corresponding solvent dimethylformamide of mass fraction, dimethyl sulfoxide (DMSO), dimethyl second The aqueous solution of acid amides or sodium sulfocyanate, 20~30 DEG C of temperature；

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

50~65 DEG C of the water temperature of the rinsing bowl；

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

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

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

8. a kind of high heat conduction polyacrylonitrile fibre according to made from preparation method any one of above claim 1-7, its It is characterized in：Contain 0.5~15% superfine graphite alkene in the high heat conduction polyacrylonitrile fibre；The high heat conduction polyacrylonitrile is fine The thermal conductivity factor of dimension is 1~5W/mk.

A kind of 9. high heat conduction polyacrylonitrile fibre according to claim 8, it is characterised in that the polyacrylonitrile it is viscous Molecular weight is 50,000~100,000；The size of the superfine graphite alkene is：Long and wide respectively 1~10 micron, thickness is received for 1~6 Rice.

A kind of 10. high heat conduction polyacrylonitrile fibre according to claim 8, it is characterised in that the high heat conduction polypropylene The filament number of nitrile fiber is 1.0~3.3dtex, and fracture strength is 2.5~6.5cN/dtex.