CN110230198A - A kind of modified carbon fiber and the preparation method and application thereof - Google Patents
A kind of modified carbon fiber and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110230198A CN110230198A CN201910648732.4A CN201910648732A CN110230198A CN 110230198 A CN110230198 A CN 110230198A CN 201910648732 A CN201910648732 A CN 201910648732A CN 110230198 A CN110230198 A CN 110230198A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- modified carbon
- preparation
- parts
- cleaned
- 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.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The present invention relates to a kind of modified carbon fibers and the preparation method and application thereof, method includes the following steps: carrying out chopping processing to carbon fiber, the length for controlling carbon fiber is 70-120mm, are placed in acetone and are stripped, clean, are dried in vacuo；Carbon fiber after drying is added in the aqueous solution being formulated by glyoxal and chitosan and is reacted, by suction filtration, retains solid, and cleaned with secondary distilled water, it is dried in vacuo, pre- modified carbon fiber is made, it is redispersed in compound surface-treating agent, it is ultrasonically treated, is filtered, drying to constant weight, high-temperature oxydation is carried out in air atmosphere, cooled to room temperature is cleaned through secondary distilled water, is dried under vacuum to constant weight.Compared with prior art, step of the present invention is simple, and controllability is good, and raw material is easy to get, and on the practicability and cost-effectiveness used, needed for complying fully with industry development really, quite has value of industrial utilization.
Description
Technical field
The invention belongs to technical field of composite materials, it is related to a kind of modified carbon fiber and the preparation method and application thereof.
Background technique
Carbon fiber is high intensity, the new fiber materials of high modulus fibre of a kind of phosphorus content 95% or more, it be by
The organic fibers such as flake graphite are piled up along fiber axial direction, through microlite obtained from carbonization and graphitization processing
Ink material.Carbon fiber has the characteristic of " soft inside despite one's hard shell ", and quality is lighter than metallic aluminium, but intensity is higher than steel, and has resistance to
The characteristic of burn into high-modulus is widely used in aerospace, advanced precision strike munitions, chemical machinery, sports equipment, the energy, vapour
The fields such as vehicle, weaving and medical instrument.It not only has the intrinsic intrinsic property of carbon material, and the softness for having both textile fabric can
Processability is reinforcing fiber of new generation.
However, the carbon fiber surface activity group of non-modified processing is few, surface inertness is big, compound often with other materials
Lyophobicity is often presented, matrix compound interface binding ability is poor, and there are more boundary defects, cannot give full play to the increasing of carbon fiber
Pretend use.Meanwhile the moisture in environment can enter in the gap formed due to well-bonded between carbon fiber and composite material,
This will be greatly reduced the mechanical property of composite material.Therefore carbon fiber surface is handled, is that carbon fiber is promoted to use development
Key.Currently, the research of carbon fiber processing method has very much, it is concentrated mainly on and handles carbon fiber surface, makes its table
The active group of mask improves its surface roughness, and then improves the adhesive strength with matrix.But existing method of modifying exists
The bulk strength of carbon fiber is also had lost while improving the surface property of carbon fiber, and aoxidizes unevenness, oxidation effectiveness is bad,
The composite property for causing its final reduces.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of simple processes, cost
It is cheap, be suitable for continuous industry and produce, controllability is good, while guaranteeing carbon fiber bulk strength, can effectively improve and resin
The modified carbon fiber and the preparation method and application thereof of basis material caking property.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of modified carbon fiber, this method specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 70-120mm, is placed in acetone, in
80-85 DEG C of extracting 3-5h, and cleaned with secondary distilled water, it is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 15-25 DEG C, 0.5-1.5h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, vacuum is dry
It is dry, pre- modified carbon fiber is made；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
The mass concentration of glyoxal is 2-4g/L in aqueous solution described in step (2), and the mass concentration of chitosan is 12-
18g/L。
The mass ratio of carbon fiber described in step (2) and chitosan is 1:3-8.
Compound surface-treating agent described in step (3) by include the raw material of following components and parts by weight content after mixing
It is prepared: 3-5 parts of glycidyl methacrylate, 1-2 parts of cocounut oil acyl diethanol amine, polyoxyethylene cetyl ether 2-3
Part, nano-cellulose 1-3,0.8-1.2 parts of sodium peroxydisulfate, 0.7-1 parts of crosslinking agent.
The diameter of the nano-cellulose is 50-80nm, length 100-300nm.
The nano-cellulose is to be chemically treated to obtain by a series of physical by native cellulose, is not only had natural
The basic structure and performance of cellulose, such as: biological degradability, sustainable reproducibility and biocompatibility also have light, high-strength
Degree, biggish surface area, higher Young's modulus, high-crystallinity and high transparency etc..
The crosslinking agent includes diacrylate -1,4- butanediol ester, butyl acrylate, ethylene glycol dimethacrylate
Or one or more of methyl methacrylate.
The condition of ultrasonic treatment described in step (3) are as follows: control supersonic frequency is 50-80KHz, and temperature is 50-65 DEG C, when
Between be 0.5-1h.
The condition of high-temperature oxydation described in step (3) are as follows: be warming up to 450-500 DEG C with 1-3 DEG C/min, constant temperature oxidation 2-
4h, then it is warming up to 540-580 DEG C with 1-3 DEG C/min, constant temperature oxidation 1-2h.
The modified carbon fiber being prepared using the above method.
The modified carbon fiber is in preparation for aerospace, chemical machinery, sports apparatus, automobile or medical instrument
Application in composite material.
In the present invention, the carbon fiber is selected from polyacrylonitrile-based carbon fibre, petroleum pitch-based carbon fiber, coal tar pitch base carbon
One or more of fiber, phenolic aldehyde base carbon fibre, cellulose base carbon fiber or lignin-base carbon fiber.In actual fabrication process
In, the vacuum degree control in the process of vacuum drying is less than -0.05MPa.
Compared with prior art, the present invention first carries out degreasing to carbon fiber surface using acetone extraction in modifying process,
Then in the aqueous solution of glyoxal and chitosan, so that the functional group on chitosan is connected with each other, to be coated on carbon fiber
Tridimensional network is formed on surface, completes the pre- modification of carbon fiber surface；Activity through pre- modified carbon fiber surface increases
By force, phenomena such as its dispersibility in compound surface-treating agent can be substantially improved, carbon fiber can be effectively prevent to gather or deposit
Occur, after under conditions of ultrasonic treatment, uniform cross-linking reaction can carried out through pre- modified carbon fiber surface, realized pair
The secondary uniform of carbon fiber coats, and ensure that the uniformity of subsequent high temperature oxidation；And during high temperature oxidation process, using rank
Section property high-temperature oxydation (aoxidizes) twice, be on the one hand conducive to carbon fiber surface once coat and secondary cladding aoxidizes mildness and
On the other hand uniformity can guarantee the adequacy of carbon fiber surface oxidation, can dramatically increase the oxygen-containing functional group of carbon fiber surface,
And then improve the chemical modification of carbon fiber and the adhesiveness with matrix resin.Preparation method step of the present invention is simple, controllably
Property it is good, raw material is easy to get, on the practicability and cost-effectiveness used, needed for complying fully with industry development really, quite have produce
Industry utility value.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 85mm, is placed in acetone, takes out in 82 DEG C
5h is mentioned, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 20 DEG C, 1h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made pre-
Modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 2.8g/L in step (2) aqueous solution, and the mass concentration of chitosan is 14.5g/
L.The mass ratio of carbon fiber and chitosan is 1:4.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 4 parts of glycidyl methacrylate, 1.4 parts of cocounut oil acyl diethanol amine, 2.2 parts of polyoxyethylene cetyl ether, Nanowire
Tie up plain 2 parts, 1 part of sodium peroxydisulfate, 0.8 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 65nm, length 120nm.Crosslinking
Agent is diacrylate -1,4- butanediol ester.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 65KHz, and temperature is 55 DEG C, time 0.7h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 480 DEG C, constant temperature oxidation 3h with 2 DEG C/min, then with 2 DEG C/min liter
Temperature is to 560 DEG C, constant temperature oxidation 1.5h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 2:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 95mm, is placed in acetone, takes out in 82 DEG C
5h is mentioned, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 20 DEG C, 1h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made pre-
Modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 3.2g/L in step (2) aqueous solution, and the mass concentration of chitosan is 15.6g/
L.The mass ratio of carbon fiber and chitosan is 1:5.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 3.8 parts of glycidyl methacrylate, 1.2 parts of cocounut oil acyl diethanol amine, polyoxyethylene cetyl ether 2.4 part, nanometer
2 parts of cellulose, 0.9 part of sodium peroxydisulfate, 0.7 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 55nm, length 180nm.
Crosslinking agent is butyl acrylate.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 70KHz, and temperature is 58 DEG C, time 0.8h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 480 DEG C, constant temperature oxidation 3h with 2 DEG C/min, then with 2 DEG C/min liter
Temperature is to 560 DEG C, constant temperature oxidation 1.5h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 3:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 100mm, is placed in acetone, in 84 DEG C
3h is extracted, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 24 DEG C, 0.6h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made
Pre- modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 2.4g/L in step (2) aqueous solution, and the mass concentration of chitosan is 13.8g/
L.The mass ratio of carbon fiber and chitosan is 1:3.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 4.2 parts of glycidyl methacrylate, 1.6 parts of cocounut oil acyl diethanol amine, polyoxyethylene cetyl ether 2.2 part, nanometer
1 part of cellulose, 0.8 part of sodium peroxydisulfate, 0.8 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 70nm, length 200nm.
Crosslinking agent is ethylene glycol dimethacrylate.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 50KHz, and temperature is 65 DEG C, time 1h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 500 DEG C, constant temperature oxidation 2h with 1 DEG C/min, then with 1 DEG C/min liter
Temperature is to 580 DEG C, constant temperature oxidation 1h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 4:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 70mm, is placed in acetone, takes out in 80 DEG C
5h is mentioned, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 25 DEG C, 0.5h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made
Pre- modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 2g/L in step (2) aqueous solution, and the mass concentration of chitosan is 12g/L.Carbon
The mass ratio of fiber and chitosan is 1:4.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 5 parts of glycidyl methacrylate, 2 parts of cocounut oil acyl diethanol amine, 3 parts of polyoxyethylene cetyl ether, nano-cellulose
2.8 parts, 1.2 parts of sodium peroxydisulfate, 1 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 70nm, length 200nm.Crosslinking agent
For methyl methacrylate.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 80KHz, and temperature is 50 DEG C, time 0.5h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 450 DEG C, constant temperature oxidation 4h with 3 DEG C/min, then with 3 DEG C/min liter
Temperature is to 540 DEG C, constant temperature oxidation 2h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 5:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 110mm, is placed in acetone, in 85 DEG C
3h is extracted, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 15 DEG C, 1.5h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made
Pre- modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 4g/L in step (2) aqueous solution, and the mass concentration of chitosan is 18g/L.Carbon
The mass ratio of fiber and chitosan is 1:8.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 3 parts of glycidyl methacrylate, 1 part of cocounut oil acyl diethanol amine, 2 parts of polyoxyethylene cetyl ether, nano-cellulose
1.5 parts, 0.8 part of sodium peroxydisulfate, 0.7 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 80nm, length 300nm.Crosslinking
Agent is diacrylate -1,4- butanediol ester.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 72KHz, and temperature is 56 DEG C, time 0.6h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 475 DEG C, constant temperature oxidation 3.6h with 2.5 DEG C/min, then with 2 DEG C/
Min is warming up to 565 DEG C, constant temperature oxidation 1.2h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 6:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 120mm, is placed in acetone, in 85 DEG C
4h is extracted, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 18 DEG C, 1.2h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made
Pre- modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 3.5g/L in step (2) aqueous solution, and the mass concentration of chitosan is 17.5g/
L.The mass ratio of carbon fiber and chitosan is 1:6.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 4.4 parts of glycidyl methacrylate, 1.3 parts of cocounut oil acyl diethanol amine, polyoxyethylene cetyl ether 2.1 part, nanometer
1.2 parts of cellulose, 1 part of sodium peroxydisulfate, 0.8 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 50nm, length 100nm.
It with butyl acrylate is that 2:1 is mixed that crosslinking agent is ethylene glycol dimethacrylate in mass ratio.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 68KHz, and temperature is 55 DEG C, time 1h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 490 DEG C, constant temperature oxidation 2.5h with 3 DEG C/min, then with 2 DEG C/min
570 DEG C are warming up to, constant temperature oxidation 1.5h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 7:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 95mm, is placed in acetone, takes out in 85 DEG C
4h is mentioned, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 20 DEG C, 1.2h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made
Pre- modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 3g/L in step (2) aqueous solution, and the mass concentration of chitosan is 16g/L.Carbon
The mass ratio of fiber and chitosan is 1:7.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 3.8 parts of glycidyl methacrylate, 1 part of cocounut oil acyl diethanol amine, 2.4 parts of polyoxyethylene cetyl ether, Nanowire
Tie up plain 2.2 parts, 1 part of sodium peroxydisulfate, 0.8 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 60nm, length 180nm.It hands over
It with diacrylate -1,4- butanediol ester is that 1:3 is mixed that connection agent is ethylene glycol dimethacrylate in mass ratio.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 70KHz, and temperature is 55 DEG C, time 1h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 460 DEG C, constant temperature oxidation 2.5h with 1 DEG C/min, then with 2 DEG C/min
560 DEG C are warming up to, constant temperature oxidation 2h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Embodiment 8:
The preparation method of the present embodiment modified carbon fiber, specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 80mm, is placed in acetone, takes out in 85 DEG C
5h is mentioned, and is cleaned with secondary distilled water, is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 25 DEG C, 1h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, is dried in vacuo, be made pre-
Modified carbon fiber；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
Wherein, the mass concentration of glyoxal is 3.6g/L in step (2) aqueous solution, and the mass concentration of chitosan is 15.4g/
L.The mass ratio of carbon fiber and chitosan is 1:4.
Step (3) compound surface-treating agent by include the raw material of following components and parts by weight content prepare after mixing and
At: 4.2 parts of glycidyl methacrylate, 1 part of cocounut oil acyl diethanol amine, 2.5 parts of polyoxyethylene cetyl ether, Nanowire
Tie up plain 2.1 parts, 0.9 part of sodium peroxydisulfate, 0.8 part of crosslinking agent.Wherein, the diameter of nano-cellulose is 75nm, length 240nm.
Crosslinking agent be methyl methacrylate, ethylene glycol dimethacrylate with butyl acrylate be in mass ratio 1:2:5 mix and
At.
The condition of step (3) ultrasonic treatment are as follows: control supersonic frequency is 70KHz, and temperature is 55 DEG C, time 1h.
The condition of step (3) high-temperature oxydation are as follows: be warming up to 480 DEG C, constant temperature oxidation 2.5h with 2 DEG C/min, then with 2 DEG C/min
570 DEG C are warming up to, constant temperature oxidation 2h.
The modified carbon fiber that the present embodiment method is prepared is used for aerospace, chemical machinery, sport device in preparation
Application in the composite material of tool, automobile or medical instrument.
Comparative example:
This comparative example is certain existing commercially available modified carbon fiber.
Composite materials property test:
By the modified carbon fiber of embodiment 1-8 and comparative example, it is woven by the way of 3 D weaving with PEEK resin silk compound
Silk (wherein, the mass ratio of PEEK resin and modified carbon fiber be 7:3) prepares the compound of carbon fiber and PEEK using mould pressing method
The exemplar size of stretching experiment requirement is made in compound by object, by universal testing machine extension test, with non-modified processing
Carbon fiber is compared with the mechanical property of the compound of PEEK, tensile strength calculated increase rate, acquired results such as table 1.
Wherein, the tensile strength of tensile strength increase rate=modified treated carbon fiber and PEEK compound/without
The carbon fiber of modification and tensile strength × 100% of PEEK compound
1 test result of table
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of modified carbon fiber, which is characterized in that this method specifically includes the following steps:
Step (1): carrying out chopping processing to carbon fiber, and the length for controlling carbon fiber is 70-120mm, is placed in acetone, in
80-85 DEG C of extracting 3-5h, and cleaned with secondary distilled water, it is dried in vacuo；
Step (2): the carbon fiber of step (1) after dry is added in the aqueous solution being formulated by glyoxal and chitosan,
At 15-25 DEG C, 0.5-1.5h is reacted, to after reaction, filter, retains solid, and cleaned with secondary distilled water, vacuum is dry
It is dry, pre- modified carbon fiber is made；
Step (3): it disperses pre- modified carbon fiber made from step (2) in compound surface-treating agent, is ultrasonically treated, mistake
Filter, drying to constant weight, and high-temperature oxydation is carried out in air atmosphere, and cooled to room temperature is cleaned through secondary distilled water, vacuum
It dries to constant weight.
2. a kind of preparation method of modified carbon fiber according to claim 1, which is characterized in that water described in step (2)
The mass concentration of glyoxal is 2-4g/L in solution, and the mass concentration of chitosan is 12-18g/L.
3. a kind of preparation method of modified carbon fiber according to claim 2, which is characterized in that carbon described in step (2)
The mass ratio of fiber and chitosan is 1:3-8.
4. a kind of preparation method of modified carbon fiber according to claim 1, which is characterized in that step is answered described in (3)
Surface modifier is closed by including that the raw material of following components and parts by weight content is prepared after mixing: Glycidyl methacrylate
3-5 parts of glyceride, 1-2 parts of cocounut oil acyl diethanol amine, 2-3 parts of polyoxyethylene cetyl ether, nano-cellulose 1-3, persulfuric acid
0.8-1.2 parts of sodium, 0.7-1 parts of crosslinking agent.
5. a kind of preparation method of modified carbon fiber according to claim 4, which is characterized in that the nano-cellulose
Diameter be 50-80nm, length 100-300nm.
6. a kind of preparation method of modified carbon fiber according to claim 4, which is characterized in that the crosslinking agent includes
One of diacrylate -1,4- butanediol ester, butyl acrylate, ethylene glycol dimethacrylate or methyl methacrylate
Or it is several.
7. a kind of preparation method of modified carbon fiber according to claim 1, which is characterized in that surpass described in step (3)
The condition of sonication are as follows: control supersonic frequency is 50-80KHz, and temperature is 50-65 DEG C, time 0.5-1h.
8. a kind of preparation method of modified carbon fiber according to claim 1, which is characterized in that with 1-3 DEG C/min heating
It is warming up to 540-580 DEG C to 450-500 DEG C, constant temperature oxidation 2-4h, then with 1-3 DEG C/min, constant temperature oxidation 1-2h.
9. the modified carbon fiber being prepared using the described in any item methods of claim 1 to 8.
10. modified carbon fiber as claimed in claim 9 preparation for aerospace, chemical machinery, sports apparatus, automobile or
Application in the composite material of medical instrument.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648732.4A CN110230198A (en) | 2019-07-18 | 2019-07-18 | A kind of modified carbon fiber and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648732.4A CN110230198A (en) | 2019-07-18 | 2019-07-18 | A kind of modified carbon fiber and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110230198A true CN110230198A (en) | 2019-09-13 |
Family
ID=67855110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910648732.4A Pending CN110230198A (en) | 2019-07-18 | 2019-07-18 | A kind of modified carbon fiber and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110230198A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139646A (en) * | 2020-01-14 | 2020-05-12 | 贵州大学 | Preparation of modified carbon fiber and nylon 6 composite material thereof |
| CN114197205A (en) * | 2022-01-19 | 2022-03-18 | 四川大学 | Modified carbon fiber and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1688799A (en) * | 1998-01-06 | 1999-07-26 | Toray Industries, Inc. | Carbon fibers and a method of producing them |
| CN105113260A (en) * | 2015-08-19 | 2015-12-02 | 上海交通大学 | Method for performing amino functionalizing on carbon fiber surface |
| CN106032410A (en) * | 2015-09-22 | 2016-10-19 | 洛阳新巨能高热技术有限公司 | Carbon fiber surface modification method |
| CN109320102A (en) * | 2018-09-17 | 2019-02-12 | 常州市群丰玻纤制品有限公司 | A kind of high-strength abrasion-proof modified glass-fiber and preparation method thereof |
-
2019
- 2019-07-18 CN CN201910648732.4A patent/CN110230198A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1688799A (en) * | 1998-01-06 | 1999-07-26 | Toray Industries, Inc. | Carbon fibers and a method of producing them |
| CN105113260A (en) * | 2015-08-19 | 2015-12-02 | 上海交通大学 | Method for performing amino functionalizing on carbon fiber surface |
| CN106032410A (en) * | 2015-09-22 | 2016-10-19 | 洛阳新巨能高热技术有限公司 | Carbon fiber surface modification method |
| CN109320102A (en) * | 2018-09-17 | 2019-02-12 | 常州市群丰玻纤制品有限公司 | A kind of high-strength abrasion-proof modified glass-fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 许跃等: "表面涂覆壳聚糖对碳纤维在水中分散性的影响", 《中国造纸》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139646A (en) * | 2020-01-14 | 2020-05-12 | 贵州大学 | Preparation of modified carbon fiber and nylon 6 composite material thereof |
| CN114197205A (en) * | 2022-01-19 | 2022-03-18 | 四川大学 | Modified carbon fiber and preparation method and application thereof |
| CN114197205B (en) * | 2022-01-19 | 2023-09-08 | 四川大学 | Modified carbon fiber and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110528314A (en) | A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown | |
| CN110016807A (en) | A kind of surface modifying method of carbon fiber surface functionalization | |
| CN107142730B (en) | A kind of method of carbon fiber surface green graft polyether amine | |
| Reddy et al. | Chemical resistance and tensile properties of glass and bamboo fibers reinforced polyester hybrid composites | |
| CN106832757A (en) | A kind of composite of Graphene phenol-formaldehyde resin modified and preparation method thereof, application | |
| CN110230198A (en) | A kind of modified carbon fiber and the preparation method and application thereof | |
| CN109233206A (en) | Plant fiber/epoxy resin composite material preparation method of rub resistance abrasion | |
| CN106149359A (en) | A kind of fire-retardant uvioresistant curtain and preparation method thereof | |
| CN109468843A (en) | A method of hydroxy-end capped dissaving polymer is grafted in carbon fiber surface | |
| CN109864042A (en) | A kind of nano-graphene preparing high thermal conductivity silk freshens food and educates silkworm method and its product | |
| CN112126096B (en) | Silk fibroin uniformly-supported graphene composite membrane, preparation method and application thereof | |
| CN107163291A (en) | A kind of carbon fiber/polyphenyl thioether composite material and preparation method thereof | |
| US5254396A (en) | Carbon fiber structure and process for producing the same | |
| CN115341390B (en) | Preparation method and application of titanium carbide MXene fiber nanocomposite | |
| CN106048764A (en) | Nanometer cellulose fiber and reinforced composite material with same | |
| CN115648739A (en) | Method for preparing carbon fiber reinforced thermoplastic resin-based felt material and composite material by suspension blending method | |
| CN104878465A (en) | Carbon nanotube regenerated bamboo fibers and production method therefor | |
| CN103174053A (en) | Production method for aramid fiber 1414 paper substrate material | |
| JP2003073932A (en) | Carbon fiber | |
| Priya et al. | Tensile, flexural, and chemical resistance properties of waste silk fabric-reinforced epoxy laminates | |
| CN105647121A (en) | Lignin fiber modified carbon fiber/epoxy resin composite material and preparation method thereof | |
| CN107722595A (en) | A kind of preparation method of the multiple dimensioned composite of graphite fiber olefinic thermoplastic polyarylether | |
| CN109422539A (en) | A kind of preparation method of alumina-silica graphene composite ceramics | |
| CN109098029A (en) | A kind of manufacturing method of novel carbon fiber heating paper | |
| CN110863341A (en) | Preparation method of PA66 grafted carbon fiber |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190913 |