CN109679200A - A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method - Google Patents

A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method Download PDF

Info

Publication number
CN109679200A
CN109679200A CN201811144853.7A CN201811144853A CN109679200A CN 109679200 A CN109679200 A CN 109679200A CN 201811144853 A CN201811144853 A CN 201811144853A CN 109679200 A CN109679200 A CN 109679200A
Authority
CN
China
Prior art keywords
carbon fiber
light weight
microporous carbon
dedicated
automotive light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201811144853.7A
Other languages
Chinese (zh)
Inventor
陈庆
曾军堂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu New Keli Chemical Science Co Ltd
Original Assignee
Chengdu New Keli Chemical Science Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu New Keli Chemical Science Co Ltd filed Critical Chengdu New Keli Chemical Science Co Ltd
Priority to CN201811144853.7A priority Critical patent/CN109679200A/en
Publication of CN109679200A publication Critical patent/CN109679200A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Abstract

The present invention proposes a kind of preparation method of dedicated microporous carbon fiber masterbatch of automotive light weight technology, the fine composite fibre of polypropylene is prepared through wet spinning technology first, obtained composite fibre is washed, elute zinc chloride, micropore is formed in cyclization, oxidation carbonization is then carried out, obtains microporous carbon fiber, and aramid fiber polymer is copolymerized in the micropore of carbon fiber, it is granulated to obtain a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology using Screw Extrusion.The carbon fiber masterbatch and polymer that the present invention obtains have excellent compatibility, and when masterbatch use, aramid fiber polymer in carbon fiber micropore is tightly combined with polymer, the present invention overcomes carbon fibers for making light weight material in automobile complex process, it is difficult to be kneaded by direct thermoplastic evenly dispersed, the poor defect of compatibility, so that carbon fiber is in automotive light weight technology application using more convenient.

Description

A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method
Technical field
The present invention relates to carbon fibre material fields, and in particular to a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and system Preparation Method.
Background technique
A kind of carbon of threadiness of carbon fiber has many excellent performances, and the axial strength and modulus of carbon fiber are high, density Low, higher than performance, no creep, superhigh temperature resistant under non-oxidizing atmosphere, fatigue durability is good, and specific heat and electric conductivity are between nonmetallic and golden Between category, thermal expansion coefficient is small and has anisotropy, and corrosion resistance is high, and X-ray transparent is good, good electrical and thermal conductivity Can, the advantages that electromagnetic wave shielding is good, be one of most important reinforcing material of advanced composite material.
The carbon fiber that polyacrylonitrile carbon fiber is produced using polyacrylonitrile as raw material, have high intensity, high-modulus, high temperature resistant, It is corrosion-resistant, antifatigue, creep resistant, conductive with the excellent performances such as thermally conductive, it is aerospace industry, indispensable engineering in automobile In addition material is also widely used in terms of machinery, sports and amusement, leisure goods, health care and civil construction, be a kind of Belong to dual-use high technical fibre.Since its production technology is relatively easy, the comprehensive performances such as good mechanical performance of product Preferably, it thus is rapidly developed, accounts for 90 ﹪ or more of the total market size.
The lightweight of automobile is under the premise of guaranteeing the intensity and security performance of automobile, and reduction automobile is whole as much as possible Standby quality reduces fuel consumption to improve the dynamic property of automobile, reduces exhaust pollution.It is demonstrated experimentally that car mass reduces by one Half, fuel consumption can also reduce nearly half.Due to environmental protection and energy-efficient needs, the lightweight of automobile has become world car The trend of development.Automotive light weight technology approach has research and development to manufacture using the material of lightweight, design optimization structure, using lightweight at present Technology.Replacing traditional metal materials using high-performance fiber enhancing composite portions is that current automobile realizes that lightweight is most effective Approach.Carbon fiber can make body of a motor car as a kind of fiber for having both intensity and quantify by force, the application of carbon fibre composite Mitigate quality 40% ~ 60%.Carbon fiber is such as used for PP, nylon thermoplastic can prepare high intensity, lightweight, resistance to height The automotive material of temperature.
For carbon fibre reinforced thermoplastics due to excellent combination property, technology development is very rapid, and composite material is being chopped Fiber and long fibre and the compound aspect of thermoplastic matrix achieve very big progress.Since thermoplastic melt viscosity is high, melting Temperature or forming temperature are high, and solvability is poor or basic insoluble in low boiling point solvent, to thermoplastic resin impregnate fiber with And processing and forming brings difficulty, also limits the application and development of thermoplastic composite.Automotive part uses carbon fiber at present The pressing mode that dimension enhancing thermoplas tic resin composite mostly takes preimpregnation, stacking to close.By carbon fiber one-way band or woven fabric Alternately laminated with resin film, then heating pressurization makes resin heating melting, and then fiber is impregnated by molten resin, carbon Fiber is equably embedded in resin film.Melt impregnation reduces ring due to not using solvent in dipping process Border pollution, saves material, improves product quality and production efficiency, and prepreg resin mass fraction control precision is high.Such as Chinese patent 201210570684X, which is disclosed, is made preimpregnation sheet material using polypropylene, carbon fiber and polyimides, wherein polypropylene Resin is impregnated in carbon fiber, and the pre-preg sheet material is then prepared into anticollision portion by cutting building materials, laying, pressing process Part.However, fiber decentralization in prepreg is low since carbon fiber surface is smooth, specific surface area is small, surface-active is low, it is used for It is poor with the cementability of matrix resin when with resin compounded, when composite molding product stress, it is easy to concentrate on not due to stress Uniformly fiber is easily caused to be drawn out, load cannot be passed, and material forms failure by shear.
It is therefore proposed that a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology, can be improved carbon fiber in thermoplastic In dispersibility and compatibility, overcome existing thermoplastic disperse carbon fibers to be difficult to disperse, the defect of poor compatibility, can further push away Carbon fiber is moved in automotive light weight technology development and application.
Summary of the invention
For current carbon fiber for making light weight material in automobile complex process, it is difficult to be kneaded by direct thermoplastic uniform Dispersion, the poor defect of compatibility, the present invention propose a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method, lead to Cross and form micropore in cyclization, solve existing thermoplastic disperse carbon fibers be difficult to disperse, the defect of poor compatibility so that Carbon fiber is in automotive light weight technology application using more convenient.
To solve the above problems, the invention adopts the following technical scheme:
A kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology, it is compound using the synthesizing chlorinated zinc of polyacrylonitrile powder Carbon fiber obtains microporous fibre using elution zinc chloride, by carbonization treatment, microporous carbon fiber is obtained, finally in microporous carbon The micropore of fiber generates polymer, is granulated to obtain the dedicated microporous carbon fiber masterbatch of the automotive light weight technology by Screw Extrusion, has Preparation is as follows:
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 76 ~ 80 DEG C, stirring and dissolving 20 ~ for 24 hours, uniform polyacrylonitrile solution is obtained, the fine compound fibre of polypropylene is prepared through wet spinning technology Dimension；
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then carry out in air atmosphere 2 ~ 5h is aoxidized, oxidizing temperature is 180 ~ 250 DEG C；
(3) the obtained oxidized fibre of step (2) is carried out low-temperature carbonization 1 ~ 2 hour under nitrogen protection, temperature be 500 DEG C~ 700 DEG C, further 1 ~ 3h of high temperature cabonization, temperature is 1300 DEG C~1500 DEG C, obtains microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 70 ~ 80 DEG C, then plus Enter catalyst sodium hypophosphite to react 1 hour under nitrogen protection, 0.15 ~ 0.5MPa pressure, under 150 ~ 180 DEG C of high temperature, after reaction Solidify 2 hours in 200 ~ 250 DEG C, 2 ~ 3 MPa, discharging；
(5) material that step (4) obtains is mixed with polymer material, additive is added, is granulated to obtain institute using Screw Extrusion State the dedicated microporous carbon fiber masterbatch of automotive light weight technology.
Preferably, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution is 45 ~ 61%, the diformazan The mass concentration of base sulfoxide is 10 ~ 25%, and the mass concentration of the zinc chloride powder is 2 ~ 13%.
Preferably, wet process spinning nozzle aperture is 60 μm, draw ratio 2:1 in wet process textile technology described in step (1), spinneret The temperature of head and conveyance conduit is maintained at 70 ~ 80 DEG C, and spinning nozzle flow is 100-119mL/h.
Preferably, the temperature of coagulating bath is 30-50 DEG C in wet process textile technology described in step (1), uses DMSO solution.
Preferably, nitrogen gas concn described in step (3) is 99.5 ~ 99.9%.
Preferably, the aperture of microporous carbon fiber described in step (3) is 10 ~ 200nm, and porosity is 5 ~ 14%.
Preferably, the mass ratio of the microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst is 3 ~ 4:5 ~ 6:5 ~ 6:1-3:0.1-0.3.
Preferably, the partial size of the microporous carbon fiber masterbatch is 0.8 ~ 1.4cm.
Preferably, the polymer material is that polyethylene, polypropylene, polyvinyl chloride, acrylonitrile-butadiene-styrene (ABS) are total The combination of one or more of polymers.
A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology is provided, be prepared by the above method by carbon fiber micropore The composite material that interior filling aramid fiber polymer and polymer are constituted.
Carbon fiber has excellent mechanical property, including high specific strength and modulus, low-density and low-heat as reinforcing material Dilatancy, heat resistance and chemical stability etc., carbon fiber possess highest absolute modulus and specific modulus, currently, commercial height The maximum intensity of strength carbon fiber is 7GPa.Carbon fiber is as a kind of high-performance reinforcement, compared with other reinforcing fibers, carbon fiber Dimension can provide highest specific modulus and specific strength.However, the dispersibility of carbon fibre reinforced composite, basic mechanical performance, all It is limited by the interfacial bond property between carbon fiber surface and resin matrix.Matrix resin contacts with each other with reinforcing fiber surface Afterwards, due to surface not be completely smooth, it is smooth, will form at uneven place mechanical interlocked.By modified carbon fiber to increase Specific surface area improves roughness, and interface cohesion can be enhanced.
In consideration of it, for current carbon fiber for making light weight material in automobile complex process, it is difficult to pass through direct thermoplastic It is kneaded evenly dispersed, the poor defect of compatibility, the present invention proposes a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and system Preparation Method.The fine composite fibre of polypropylene of surface micropore is prepared first, is then carbonized, obtains micro- under nitrogen protection Hole carbon fiber, it is finally that microporous carbon fiber and phthalic acid, water, hexamethylene diamine aqueous dispersion is uniform, it is anti-that catalyst is then added Answer, solidify after discharge, be granulated to obtain a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology using Screw Extrusion.By poly- third The fine fiber of alkene forms micropore, to make carbon fiber, there are micropores, and aramid fiber polymer is copolymerized in the micropore of carbon fiber, into And realize mechanical interlocked, masterbatch is added in polymeric matrix, obtained carbon fiber masterbatch and polymer are with excellent compatible Property, and then improve the mechanical property of automobile carbon fibre reinforced composite.
The present invention provides a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method, compared with prior art, Its feature protruded and excellent effect are:
1, the present invention proposes a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method, contains micropore poly- third by preparation The fine fiber of alkene, prepares the carbon fiber there are micropore, and aramid fiber polymer, obtained carbon fiber are copolymerized in the micropore of carbon fiber Tieing up masterbatch and polymer has an excellent compatibility, and the masterbatch is in use, aramid fiber polymer in carbon fiber micropore Be tightly combined with polymer, solve existing thermoplastic disperse carbon fibers be difficult to disperse, the defect of poor compatibility.
2, present invention process step is simple, improves production efficiency, the masterbatch property of preparation is stablized, so that carbon fiber is in vapour It is easy to transport using more convenient in vehicle lightweight application, is suitable for large-scale production.
3, by masterbatch prepared by the present invention be used for produce automobile component excellent in mechanical performance, ensure that automobile intensity and Security performance reduces the kerb weight of automobile, so as to reduce fuel consumption, reduce exhaust pollution can, realize section The purpose of energy environmental protection.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 76 DEG C, is stirred It mixes dissolution for 24 hours, obtains uniform polyacrylonitrile solution, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution It is 51%, the mass concentration of the dimethyl sulfoxide is 15%, and the mass concentration of the zinc chloride powder is 10%, and setting wet process is sprayed Silk oral pore diameter is 60 μm, draw ratio 2:1, and the temperature of spinning head and conveyance conduit is maintained at 73 DEG C, and spinning nozzle flow is 119mL/ H carries out coagulating bath using DMSO solution, and the temperature of coagulating bath is 37 DEG C, and it is fine multiple that polypropylene is prepared through wet spinning technology Condensating fiber.
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then in air atmosphere Oxidation 5h is carried out, oxidizing temperature is 190 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 1.4 hours under nitrogen protection, temperature is 540 DEG C, Further high temperature cabonization 1h, temperature are 1500 DEG C, and obtaining aperture is 110nm, and porosity is 14% microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 70 DEG C, is then added and urges Agent sodium hypophosphite makes the mass ratio 4 of microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It reacts 1 hour under 5:5:3:0.1,0.15MPa pressure, under 170 DEG C of high temperature, solidifies 2 hours after reaction in 230 DEG C, 2.5 MPa, Discharging；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant 0.5%, antioxidant 0.2%, coupling agent 0.3% mixes, and is granulated to obtain the dedicated micropore carbon fiber of automotive light weight technology that partial size is 1.4cm using Screw Extrusion Tie up masterbatch.
Embodiment 2
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 79 DEG C, is stirred Dissolution 22h is mixed, uniform polyacrylonitrile solution, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution are obtained It is 45%, the mass concentration of the dimethyl sulfoxide is 13%, and the mass concentration of the zinc chloride powder is 12%, and setting wet process is sprayed Silk oral pore diameter is 60 μm, draw ratio 2:1, and the temperature of spinning head and conveyance conduit is maintained at 80 DEG C, and spinning nozzle flow is 104mL/ H carries out coagulating bath using DMSO solution, and the temperature of coagulating bath is 30 DEG C, and it is fine multiple that polypropylene is prepared through wet spinning technology Condensating fiber.
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then in air atmosphere Oxidation 3.5h is carried out, oxidizing temperature is 210 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 1.5 hours under nitrogen protection, temperature is 500 DEG C, Further high temperature cabonization 3h, temperature are 1300 DEG C, and obtaining aperture is 80nm, and porosity is 10% microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 74 DEG C, is then added and urges Agent sodium hypophosphite makes the mass ratio 4 of microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It reacts 1 hour under 6:6:3:0.2,0.34MPa pressure, under 175 DEG C of high temperature, solidifies 2 hours after reaction in 240 DEG C, 2.5 MPa, Discharging；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant polyethylene wax 0.5% resist Oxygen agent 0.2%, silane coupling agent 0.3% mix, and it is dedicated to be granulated to obtain the automotive light weight technology that partial size is 1.0cm using Screw Extrusion Microporous carbon fiber masterbatch.
Embodiment 3
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 80 DEG C, is stirred It mixes dissolution for 24 hours, obtains uniform polyacrylonitrile solution, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution It is 60%, the mass concentration of the dimethyl sulfoxide is 23%, and the mass concentration of the zinc chloride powder is 2%, and wet process spinneret is arranged Oral pore diameter is 60 μm, draw ratio 2:1, and the temperature of spinning head and conveyance conduit is maintained at 70 DEG C, and spinning nozzle flow quantity is 114mL/ H carries out coagulating bath using DMSO solution, and the temperature of coagulating bath is 50 DEG C, and it is fine multiple that polypropylene is prepared through wet spinning technology Condensating fiber.
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then in air atmosphere Oxidation 2.3h is carried out, oxidizing temperature is 200 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 1 hour under nitrogen protection, temperature is 700 DEG C, into One step high temperature cabonization 2.5h, temperature are 1450 DEG C, and obtaining aperture is 10nm, and porosity is 12% microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 78 DEG C, is then added and urges Agent sodium hypophosphite makes the mass ratio 4 of microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It is reacted 1 hour under 5:5:3:0.3,0.5MPa pressure, under 160 DEG C of high temperature, in 200 DEG C, 3 MPa solidification 2 hours after reaction, out Material；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant 0.5%, antioxidant 0.2%, coupling agent 0.3% mixes, and is granulated to obtain the dedicated micropore carbon fiber of automotive light weight technology that partial size is 0.8cm using Screw Extrusion Tie up masterbatch.
Embodiment 4
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 79 DEG C, is stirred It mixes dissolution for 24 hours, obtains uniform polyacrylonitrile solution, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution It is 56%, the mass concentration of the dimethyl sulfoxide is 25%, and the mass concentration of the zinc chloride powder is 3%, and wet process spinneret is arranged Oral pore diameter is 60 μm, draw ratio 2:1, and the temperature of spinning head and conveyance conduit is maintained at 73 DEG C, and spinning nozzle flow is 104mL/h, Coagulating bath is carried out using DMSO solution, the temperature of coagulating bath is 36 DEG C, and it is fine compound that polypropylene is prepared through wet spinning technology Fiber.
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then in air atmosphere Oxidation 2h is carried out, oxidizing temperature is 250 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 1.3 hours under nitrogen protection, temperature is 560 DEG C, Further high temperature cabonization 2.6h, temperature are 1410 DEG C, and obtaining aperture is 200nm, and porosity is 11% microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 80 DEG C, is then added and urges Agent sodium hypophosphite makes the mass ratio 4 of microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It reacts 1 hour under 5:5:2:0.1,0.45MPa pressure, under 150 DEG C of high temperature, solidifies 2 hours after reaction in 210 DEG C, 2.4 MPa, Discharging；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant 0.5%, antioxidant 0.2%, coupling agent 0.3% mixes, and is granulated to obtain the dedicated microporous carbon of automotive light weight technology that partial size is 0.95cm using Screw Extrusion Fiber master batch.
Embodiment 5
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 79 DEG C, is stirred Dissolution 23h is mixed, uniform polyacrylonitrile solution, the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution are obtained It is 61%, the mass concentration of the dimethyl sulfoxide is 10%, and the mass concentration of the zinc chloride powder is 13%, and setting wet process is sprayed Silk oral pore diameter is 60 μm, draw ratio 2:1, and the temperature of spinning head and conveyance conduit is maintained at 72 DEG C, and spinning nozzle flow is 100mL/ H carries out coagulating bath using DMSO solution, and the temperature of coagulating bath is 48 DEG C, and it is fine multiple that polypropylene is prepared through wet spinning technology Condensating fiber.
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then in air atmosphere Oxidation 5h is carried out, oxidizing temperature is 180 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 2 hours under nitrogen protection, temperature is 520 DEG C, into One step high temperature cabonization 1.4h, temperature are 1350 DEG C, and obtaining aperture is 180nm, and porosity is 5% microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 78 DEG C, is then added and urges Agent sodium hypophosphite makes the mass ratio 4 of microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It is reacted 1 hour under 6:6:3:0.1,0.45MPa pressure, under 180 DEG C of high temperature, in 250 DEG C, 2 MPa solidification 2 hours after reaction, out Material；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant polyethylene wax 0.5%, 1010 antioxidant 0.2%, titanate coupling agent 0.3% mix, and are granulated to obtain the automobile that partial size is 0.12cm using Screw Extrusion The dedicated microporous carbon fiber masterbatch of lightweight.
Comparative example 1
(1) polyacrylonitrile powder, dimethyl sulfoxide and appropriate amount of deionized water are weighed, using heating water bath to 79 DEG C, stirring and dissolving 23h obtains uniform polyacrylonitrile solution, and the mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution is 61%, The mass concentration of the dimethyl sulfoxide is 10%, and setting wet process spinning nozzle aperture is 60 μm, draw ratio 2:1, spinning head and conveying The temperature of pipeline is maintained at 72 DEG C, and spinning nozzle flow is 100mL/h, carries out coagulating bath, the temperature of coagulating bath using DMSO solution It is 48 DEG C, the fine composite fibre of polypropylene is prepared through wet spinning technology.
(2) it will be washed through the composite fibre that step (1) obtains, and then carry out oxidation 5h, oxidizing temperature in air atmosphere It is 180 DEG C；
(3) the obtained oxidized fibre of step (2) being carried out low-temperature carbonization 2 hours under nitrogen protection, temperature is 520 DEG C, into One step high temperature cabonization 1.4h, temperature are 1350 DEG C, obtain carbon fiber；
(4) carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 78 DEG C, catalyst is then added Sodium hypophosphite makes the mass ratio 4:6:6:3 of carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst in nitrogen protection: It reacts 1 hour, solidifies 2 hours after reaction in 250 DEG C, 2 MPa, discharging under 0.1,0.45MPa pressure, under 180 DEG C of high temperature；
(5) material 60% and polypropylene 39% for obtaining step (4) according to mass percent, lubricant polyethylene wax 0.5%, 1010 antioxidant 0.2%, titanate coupling agent 0.3% mix, and are granulated to obtain the carbon fiber that partial size is 0.12cm using Screw Extrusion Tie up masterbatch.
Comparative example 1 is not handled carbon fiber microporous.
Comparative example 2
According to mass percent by commercially available T300 carbon fiber 30% and polypropylene 69%, lubricant polyethylene wax 0.5%, 1010 antioxygens Agent 0.2%, titanate coupling agent 0.3% mix, and are granulated to obtain the carbon fiber masterbatch that partial size is 0.12cm using Screw Extrusion.
By the obtained masterbatch of embodiment 1-5, comparative example 1-2 and ABS, PP, nano talc, titanate coupling agent with quality It is mixed than 10:52:20:15:3, mixing extrusion, test specimens is made, test tensile strength, room temperature notch impact strength, cantilever beam Impact strength, such as table 1.
Table 1:
Sample Tensile strength MPa Notch impact strength J/m2 Cantilever beam impact strength J/m
Embodiment 1 82 99 825
Embodiment 2 77 97 886
Embodiment 3 87 95 837
Embodiment 4 82 92 868
Embodiment 5 85 95 893
Comparative example 1 63 83 785
Comparative example 2 59 75 655

Claims (10)

1. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology, which is characterized in that it is specific the preparation method is as follows:
(1) polyacrylonitrile powder, dimethyl sulfoxide, zinc chloride and appropriate amount of deionized water are weighed, using heating water bath to 76 ~ 80 DEG C, stirring and dissolving 20 ~ for 24 hours, uniform polyacrylonitrile solution is obtained, the fine compound fibre of polypropylene is prepared through wet spinning technology Dimension；
(2) it will be washed through the composite fibre that step (1) obtains, and elute zinc chloride, form micropore, then carry out in air atmosphere 2 ~ 5h is aoxidized, oxidizing temperature is 180 ~ 250 DEG C；
(3) the obtained oxidized fibre of step (2) is carried out low-temperature carbonization 1 ~ 2 hour under nitrogen protection, temperature be 500 DEG C~ 700 DEG C, further 1 ~ 3h of high temperature cabonization, temperature is 1300 DEG C~1500 DEG C, obtains microporous carbon fiber；
(4) microporous carbon fiber that step (3) obtains is uniformly dispersed with phthalic acid, water, hexamethylene diamine at 70 ~ 80 DEG C, then plus Enter catalyst sodium hypophosphite to react 1 hour under nitrogen protection, 0.15 ~ 0.5MPa pressure, under 150 ~ 180 DEG C of high temperature, after reaction Solidify 2 hours in 200 ~ 250 DEG C, 2 ~ 3 MPa, discharging；
(5) material that step (4) obtains is mixed with polymer material, additive is added, is granulated to obtain institute using Screw Extrusion State the dedicated microporous carbon fiber masterbatch of automotive light weight technology.
2. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology as described in claim 1, which is characterized in that The mass concentration of polyacrylonitrile powder described in the polyacrylonitrile solution is 45 ~ 61%, the mass concentration of the dimethyl sulfoxide It is 10 ~ 25%, the mass concentration of the zinc chloride powder is 2 ~ 13%.
3. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology as described in claim 1, which is characterized in that Wet process spinning nozzle aperture is 60 μm, draw ratio 2:1 in wet process textile technology described in step (1), spinning head and conveyance conduit Temperature is maintained at 70 ~ 80 DEG C, and spinning nozzle flow is 100-119mL/h.
4. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology as claimed in claim 3, which is characterized in that The temperature of coagulating bath is 30-50 DEG C in wet process textile technology described in step (1), uses DMSO solution.
5. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology according to claim 1, feature exist In nitrogen gas concn described in step (3) is 99.5 ~ 99.9%.
6. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology as described in claim 1, which is characterized in that The aperture of microporous carbon fiber described in step (3) is 10 ~ 200nm, and porosity is 5 ~ 14%.
7. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology according to claim 1, feature exist In the mass ratio of the microporous carbon fiber and phthalic acid, hexamethylene diamine, water, catalyst is 3 ~ 4:5 ~ 6:5 ~ 6:1-3:0.1- 0.3。
8. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology according to claim 1, feature exist In the partial size of the microporous carbon fiber masterbatch is 0.8 ~ 1.4cm.
9. a kind of preparation method of the dedicated microporous carbon fiber masterbatch of automotive light weight technology according to claim 1, feature exist In the polymer material is one of polyethylene, polypropylene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer Or two or more combination.
10. a kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology, which is characterized in that described in any item by claim 1-9 Method is prepared.
CN201811144853.7A 2018-09-29 2018-09-29 A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method Withdrawn CN109679200A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811144853.7A CN109679200A (en) 2018-09-29 2018-09-29 A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811144853.7A CN109679200A (en) 2018-09-29 2018-09-29 A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method

Publications (1)

Publication Number Publication Date
CN109679200A true CN109679200A (en) 2019-04-26

Family

ID=66185618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811144853.7A Withdrawn CN109679200A (en) 2018-09-29 2018-09-29 A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method

Country Status (1)

Country Link
CN (1) CN109679200A (en)

Similar Documents

Publication Publication Date Title
Yao et al. Comparison of carbon nanotubes and graphene oxide coated carbon fiber for improving the interfacial properties of carbon fiber/epoxy composites
CN103665769B (en) The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre
KR101146612B1 (en) Prepreg, preform, molded product, and method for manufacturing prepreg
CN104277421A (en) Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material
CN107057283B (en) A kind of carbon fiber enhancement resin base composite material and preparation method thereof
CN105968718A (en) Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material
Mahltig et al. Inorganic and composite fibers: production, properties, and applications
TW201634782A (en) Sizing-agent-coated carbon fibers, process for producing sizing-agent-coated carbon fibers, carbon-fiber-reinforced composite material, and process for producing carbon-fiber-reinforced composite material
CN101343409A (en) Carbon fiber reinforced composite and preparation thereof
Shaikh et al. Progress in carbon fiber and its polypropylene-and polyethylene-based composites
CN109206905B (en) Graphene bismaleimide resin composite material and preparation method thereof
JP2013122105A (en) Hollow fiber having gradient property and method for producing the same
CN107177985A (en) A kind of preparation method of the aramid fiber two-bath gum dipping liquid of modified zinc oxide
CN105733096A (en) Long carbon fiber reinforced thermoplastic composite material and preparation method thereof
CN104017334A (en) High-modulus sheet molding compound (SMC) and production method thereof
CN105690802B (en) A kind of preparation method and application of carbon fibre reinforced high-molecular based composites
CN108752611A (en) A kind of aramid nano-fiber hybrid film of high strength and preparation method thereof
CN107722595B (en) Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material
CN104356585A (en) High-performance continuous carbon fiber reinforced ABS composite material and preparation method thereof
KR102191092B1 (en) Thermoplastic resin matrix fiber and carbon fiber-reinforced thermoplastic plastic composite having excellent impregnation property produced therefrom and manufacturing method thereof
CN111320841B (en) Aramid fiber/carbon nanotube composite reinforced carbon fiber resin prepreg
CN109679200A (en) A kind of dedicated microporous carbon fiber masterbatch of automotive light weight technology and preparation method
CN107880483A (en) A kind of preparation method of graphene phenol-formaldehyde resin modified
JP6549814B1 (en) Carbon fiber bundle, prepreg, fiber reinforced composite material
CN108504031A (en) A kind of preparation method of graphene oxide/phenolic resin film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190426