CN112080101B - Carbon fiber composite material and preparation method thereof, and reinforced ultrahigh molecular weight polyethylene composition containing carbon fiber composite material and preparation method thereof - Google Patents

Carbon fiber composite material and preparation method thereof, and reinforced ultrahigh molecular weight polyethylene composition containing carbon fiber composite material and preparation method thereof Download PDF

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CN112080101B
CN112080101B CN202010996228.6A CN202010996228A CN112080101B CN 112080101 B CN112080101 B CN 112080101B CN 202010996228 A CN202010996228 A CN 202010996228A CN 112080101 B CN112080101 B CN 112080101B
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carbon fiber
composite material
fiber composite
molecular weight
parts
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CN112080101A (en
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赵景峰
赵海峰
赵耀鑫
师兵强
张营飞
王梦尧
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Yunnan Xinke New Material Engineering Technology Co ltd
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract

The invention relates to the technical field of polyethylene, and discloses a carbon fiber composite material which comprises a flexible body and modified carbon fibers dispersed in the flexible body, wherein the modified carbon fibers account for 50-70% of the flexible body, and the balance is the flexible body; the flexible body comprises polyurethane acrylate, and the modified carbon fiber is inorganic nano particle grafted carbon fiber. The reinforced ultrahigh molecular weight polyethylene composition comprises, by weight, 100 parts of ultrahigh molecular weight polyethylene, 10-20 parts of low density polyethylene, 10-60 parts of carbon fiber composite material, 0.5-3 parts of coupling agent, 0.5-5 parts of antioxidant and 2-4 parts of lubricant. Also disclosed are methods of making the compositions. The carbon fiber composite material of the application reaches the advantages of good stability, excellent thermal stability and suitability for processing of improving the strength of the carbon fiber, the carbon fiber and the base resin. The carbon fiber composite material is applied to the ultra-high molecular weight polyethylene to improve the weather resistance and the mechanical property of the ultra-high molecular weight polyethylene.

Description

Carbon fiber composite material and preparation method thereof, and reinforced ultrahigh molecular weight polyethylene composition containing carbon fiber composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polyethylene, and particularly relates to a carbon fiber composite material and a preparation method thereof, a reinforced ultra-high molecular weight polyethylene composition containing the carbon fiber composite material and a preparation method of the reinforced ultra-high molecular weight polyethylene composition.
Background
Currently, carbon fibers are added into ultra-high molecular weight polyethylene to form a resin matrix composite material so as to improve the mechanical properties of resin. Because the interface interaction between the carbon fiber and the polyethylene resin is weak, the carbon fiber cannot be well dispersed in the polyethylene resin, and the following technical means are adopted for improvement in the prior art: (1) etching the carbon fibers to improve the roughness of the surfaces of the carbon fibers, so that a physical adsorption effect is formed between the carbon fibers and the polyethylene resin conveniently; (2) the flexible polymer is grafted on the carbon fiber, and the flexible polymer and the polyethylene resin form a mechanical interlocking effect, so that the interface strength between the carbon fiber and the polyethylene resin is enhanced, and due to the ductility of the length of the flexible polymer chain, the resin matrix composite material can transmit stress to the carbon fiber through the flexible polymer chain in a stress process, so that the purpose of stress dispersion is achieved; (3) and adding an interface modifier, wherein the interface modifier mostly adopts a silane coupling agent, and can simultaneously modify the surfaces of the carbon fibers and the polyethylene resin so that the polyethylene resin and the carbon fibers are grafted to form a copolymer.
The above-mentioned improvement has the following disadvantages; (1) after the carbon fibers are etched, the disordered structure in the carbon fibers is exposed, so that the tensile strength of the carbon fibers is reduced, and the strength of the resin matrix composite material is reduced; (2) after the carbon fiber is grafted with the flexible polymer, the tensile strength is reduced; (3) when the silane coupling agent is used for modification, the polyolefin structure of the polyethylene has no active group, so that a chemical bond cannot be formed with the silane coupling agent, and the connection strength between the polyethylene resin and the carbon fiber is weak.
Therefore, how to overcome the above disadvantages is a problem that needs to be solved urgently. Patent document 1 provides a reinforcing filler for solving the above problems.
< patent document >
Patent document 1: publication No. CN111356723A
Patent document 1 provides a polyvinyl alcohol-sized filler for reinforcing plastics, which uses polyvinyl alcohol and a copolymer thereof, or silane-modified polyvinyl alcohol as a filler and is applicable to a base resin. The polyvinyl alcohol is a film forming agent, has certain adhesion and strength, and when the polyvinyl alcohol is applied to carbon fibers and a resin substrate, the bonding degree of the polyvinyl alcohol and the carbon fibers is poor, although the polyvinyl alcohol can be subjected to silane modification treatment, the polyvinyl alcohol after silane modification is only connected together through partial chemical adsorption and physical adsorption, and does not contribute too much to the interface interaction between the carbon fibers and the substrate resin. Because the base resin is mostly prepared by extrusion and melting, the polyvinyl alcohol is thermally decomposed under the action of high temperature, so that the action strength between the polyvinyl alcohol and the carbon fiber and the base resin is easily reduced.
In view of this, a modified material is provided that enhances the interfacial strength and thermal stability between the carbon fibers and the matrix resin.
Disclosure of Invention
The invention aims to provide a carbon fiber composite material, which is used for solving the technical problems of poor thermal stability and poor connection firmness of carbon fibers and base resin.
The carbon fiber composite material comprises a flexible body and modified carbon fibers dispersed in the flexible body, wherein the modified carbon fibers account for 50% -70% of the flexible body, and the balance of the flexible body according to volume fraction; the flexible body comprises polyurethane acrylate, and the modified carbon fiber is inorganic nano particle grafted carbon fiber.
The carbon fiber grafted inorganic nanoparticles can improve the mechanical property of carbon fibers, and can improve the combination effect of the carbon fibers and base resin in the processes of carbon fiber grafting, modification or etching, but damage the carbon fiber structure to cause the reduction of mechanical properties such as tensile strength of the carbon fibers, so that the problem of the reduction of the tensile strength of the carbon fibers after modification treatment can be solved by grafting the carbon fibers with the inorganic nanoparticles. The modified carbon fibers are subjected to dispersion modification treatment through urethane acrylate to obtain the composite material, and the bonding firmness between the carbon fibers and the base material resin can be improved. This is due to the unique hard and soft block structure of the urethane acrylate, which provides matrix strength and thermal stability, and soft block structure which provides matrix flexibility and ductility. Active groups in the polyurethane acrylate can be grafted with inorganic nano particles and carbon fibers, so that the firmness is improved. After the carbon fiber composite material and the base material resin are blended to form a mixed system, under the action of environmental force, the base material resin transfers stress to the carbon fibers through an interface interaction part, and the function of stress dispersion is achieved. Because the polyurethane acrylate has certain strength, the condition that the interface is broken when the stress of the environment force on the interface is concentrated can be avoided. The polyurethane acrylate has wide processing temperature and acid and alkali resistance, and can not be thermally degraded when being applied to base material resin. In addition, due to the existence of the inorganic nanoparticles on the carbon fibers, the inorganic nanoparticles can play a role in modifying the polyurethane acrylate, so that the strength and the weather resistance of the polyurethane acrylate are improved.
The invention further aims to provide a preparation method of the carbon fiber composite material, which has the advantages of simple preparation method and less working procedures.
Specifically, the preparation method of the carbon fiber composite material comprises the step of carrying out ultrasonic stirring treatment on the flexible body and the modified carbon fiber, wherein the ultrasonic time is 40-60 min, and the temperature is 60-80 ℃.
The invention further aims to provide a reinforced ultra-high molecular weight polyethylene composition for solving the problems of poor mechanical property and poor weather resistance of the existing polyethylene plate, and the reinforced ultra-high molecular weight polyethylene composition has the advantages of good stability, wear resistance, corrosion resistance and high strength.
The reinforced ultrahigh molecular weight polyethylene composition is characterized by comprising, by weight, 100 parts of ultrahigh molecular weight polyethylene, 10-20 parts of low density polyethylene, 10-60 parts of carbon fiber composite material, 0.5-3 parts of coupling agent, 0.5-5 parts of antioxidant and 2-4 parts of lubricant.
A further object of the present invention is to provide a method for preparing an enhanced ultra-high molecular weight polyethylene composition, which has the advantages of simple preparation method, few processes, and improved processing efficiency.
Specifically, the preparation method of the reinforced ultra-high molecular weight polyethylene composition comprises the following steps:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound; hot-pressing and cold-pressing the rubber compound
The beneficial effects of the invention are as follows:
the carbon fiber composite material of the application reaches the advantages of good stability, excellent thermal stability and suitability for processing of improving the strength of the carbon fiber, the carbon fiber and the base resin. The carbon fiber composite material is applied to the ultra-high molecular weight polyethylene, so that the processing fluidity can be improved, and the weather resistance and the mechanical property of the ultra-high molecular weight polyethylene can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a carbon fiber composite material, which comprises a flexible body and modified carbon fibers dispersed in the flexible body, wherein the modified carbon fibers account for 35-50% of the flexible body, and the balance is the flexible body; the flexible body comprises polyurethane acrylate, and the modified carbon fiber is inorganic nano particle grafted carbon fiber.
According to the invention, the flexible body also comprises epoxy resin, wherein the epoxy resin accounts for 3-6% of the flexible body according to volume fraction, and the balance is polyurethane acrylate. The polar group in the molecular structure of the urethane acrylate can react with a substance containing active hydrogen, such as polyethylene resin, to form a chemical bond with larger bond energy, so that the adhesion performance of the urethane acrylate is improved. However, since the initial tack of urethane acrylate is not high, the bonding strength between the carbon fibers and the matrix resin is likely to be low during the initial use. Therefore, the polyurethane acrylate is modified by adopting a mode of adding the epoxy resin, the epoxy resin has good adhesive property, high strength and good corrosion resistance, and the adhesive property of the polyurethane acrylate can be improved. The epoxy resin is beneficial to mixing, interaction and entanglement between polyurethane and polyacrylate in the polyurethane acrylate, and the epoxy resin/the polyurethane acrylate form a cross-linked network structure, so that the thermal stability, the mechanical property and the bonding property of the flexible body can be enhanced. Meanwhile, the epoxy resin also has the high-temperature resistance characteristic, and the high-temperature resistance of the polyurethane acrylate can be improved. In addition, the epoxy resin can improve the fluidity of the mixed system, so that the base material resin is easy to process. The carbon fiber/inorganic nano particle and the epoxy resin form a chemical bond, and the bond energy further improves the connection strength of the carbon fiber and the base material fiber. If the addition amount of the epoxy resin is too large, the viscosity of the system is increased, so that the processability of the carbon fiber composite material and the matrix resin is poor, the epoxy resin is easy to be separated from the urethane acrylate, and the bonding strength is further reduced.
In the invention, the polyurethane acrylate is obtained by modifying polyurethane with methyl methacrylate and butyl acrylate. The methyl methacrylate and the butyl acrylate contain ionizable functional groups such as carboxyl groups and sulfonic acid groups, and the ionizable functional groups are introduced into the side chain of the polyurethane prepolymer after the reaction with polyurethane, so that the polyurethane acrylate with low temperature resistance, excellent mechanical property, good flexibility and good adhesive force is formed.
The preparation method of the polyurethane acrylate comprises the following steps: adding polyisocyanate and polyether glycol into acetone, heating to 50-70 ℃, adding a tin catalyst, heating to 70-90 ℃, and stirring at constant temperature for 2-5 h; cooling to 50-70 ℃, adding methyl methacrylate and butyl acrylate, continuing to react for 2-5 h, adding a neutralizing agent, reacting for 20-40 min, adding deionized water, and stirring at high speed to obtain an emulsion with the solid content of 40-80%. The mass ratio of acetone, polyisocyanate, polyether glycol, tin catalyst, methyl methacrylate, butyl acrylate and neutralizer is (1-5); the stirring speed is 1000 r/min-3000 r/min.
The preparation method of the modified carbon fiber comprises the steps of dispersing inorganic nanoparticles in an organic solvent, wherein the organic solvent is a mixed solution of absolute ethyl alcohol and a silane coupling agent, the volume ratio of the absolute ethyl alcohol to the silane coupling agent is 3-0.05, adding the carbon fiber, carrying out ultrasonic oscillation treatment for reaction, and repeatedly carrying out suction filtration by using the absolute ethyl alcohol after the reaction to obtain the carbon fiber grafted with the inorganic nanoparticles. The ultrasonic treatment time is 20-40 min, and the temperature is 80-120 ℃. The mass ratio of the carbon fiber to the inorganic nanoparticles to the organic solvent is 10-30.
In the invention, the inorganic nano-particles are TiO 2 、SiO 2 MgO, znO or silica sol.
In the present invention, the carbon fibers are etched to enhance the bonding strength between the carbon fibers and the base resin, and the etching may be performed by a conventional electrochemical method, a plasma method, a coating method, or the like. After the carbon fiber is etched, the condition that the tensile strength of the carbon fiber is reduced after the carbon fiber is etched can be compensated due to the sum of bonds of the carbon fiber and the inorganic nano particles.
In the present invention, the silane coupling agent may be a silane coupling agent commonly used in the art, and may also be an organosilicon peroxide coupling agent.
Secondly, the invention provides a preparation method of the carbon fiber composite material, which is characterized in that the flexible body and the modified carbon fiber are subjected to ultrasonic stirring treatment, wherein the ultrasonic time is 40-60 min, and the temperature is 60-80 ℃.
The invention provides a reinforced ultra-high molecular weight polyethylene composition, which comprises 100 parts by weight of ultra-high molecular weight polyethylene, 10-20 parts by weight of low density polyethylene, 10-60 parts by weight of carbon fiber composite material, 0.5-3 parts by weight of coupling agent, 0.5-5 parts by weight of antioxidant and 2-4 parts by weight of lubricant.
In the invention, the coupling agent is an organosilicon peroxide coupling agent.
In the invention, the organosilicon peroxide coupling agent is vinyl tributyl peroxy silane.
This is because the conventional silane coupling agent has poor adhesion to substances with weak polarity or non-polarity, and although the modified carbon fiber and the base resin can be modified by using the conventional silane coupling agent to bond the modified carbon fiber and the base resin, the polyethylene is a non-polar group, so that the bonding strength between the modified carbon fiber and the base resin is poor, and the bonding strength and the strength cannot be further improved. But adopt organosilicon peroxide coupling agent can carry out fine coupling effect to both, this is because carbon fiber and substrate resin are in the course of working, the high temperature that processing produced makes organosilicon peroxide coupling agent take place thermal decomposition, generate active free radical after the peroxide bond fracture, the free radical not only can make modified carbon fiber and substrate resin couple, simultaneously because still including the flexible body in the mixed system, can also make between each component of flexible body, take place to couple between flexible body and the substrate resin, further promote the coupling effect of mixed system. The organosilicon peroxide coupling agent is vinyl tributyl peroxy silane.
Fourthly, the invention provides a preparation method of the reinforced ultra-high molecular weight polyethylene composition, which comprises the following steps:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound;
and (4) carrying out hot press molding and cold press molding on the rubber compound to obtain the enhanced ultrahigh molecular weight polyethylene composition.
In the invention, the banburying temperature is 120-170 ℃ and the banburying time is 3-5 min.
< example >
Example 1
The carbon fiber composite material comprises 55% of polyurethane acrylate and the balance of modified carbon fiber in volume fraction.
The preparation method of the polyurethane acrylate comprises the steps of adding polyisocyanate and polyether glycol into acetone, heating to 60 ℃, adding a tin catalyst, heating to 80 ℃, and stirring at constant temperature for 3 hours; cooling to 60 ℃, adding methyl methacrylate and butyl acrylate, continuing to react for 3h, adding a neutralizing agent, reacting for 25min, adding deionized water, and stirring at high speed to obtain an emulsion with the solid content of 55%. The mass ratio of acetone, polyisocyanate, polyether glycol, tin catalyst, methyl methacrylate, butyl acrylate and neutralizer is 3; the stirring speed was 2000r/min.
The preparation method of the modified carbon fiber comprises the following steps of 2 Dispersing in an organic solvent, wherein the organic solvent is a mixed solution of absolute ethyl alcohol and a silane coupling agent, the volume ratio of the absolute ethyl alcohol to the silane coupling agent is 3 2 The carbon fiber of (1); carbon fiber SiO 2 The mass ratio of the organic solvent is 25; the ultrasonic treatment time is 25min, and the temperature is 100 ℃.
The preparation method of the carbon fiber composite material comprises the steps of carrying out ultrasonic stirring treatment on the polyurethane acrylate and the modified carbon fiber, wherein the ultrasonic time is 25min, and the temperature is 80 ℃.
Example 2
The present example is different from example 1 in that the carbon fiber composite material contains 70% of modified carbon fiber in terms of volume fraction, and the balance is urethane acrylate.
Example 3
The present example is different from example 1 in that the carbon fiber composite material contains 50% by volume of the modified carbon fiber and the balance of urethane acrylate.
Example 4
This example differs from example 1 in that the solids content of the urethane acrylate is 75%.
Example 5
This example differs from example 1 in that the solids content of the urethane acrylate is 45%.
Example 6
This example differs from example 1 in that the modified carbon fiber is prepared by a process in which SiO is the carbon fiber 2 The mass ratio of the organic solvent is 30.
Example 7
This example differs from example 1 in that the modified carbon fiber is prepared by a process in which SiO is the carbon fiber 2 The mass ratio of the organic solvent is 10.
Example 8
This example differs from example 1 in that SiO is added 2 Instead of silica sol, in another embodiment TiO may be substituted 2 MgO or ZnO.
Example 9
This example differs from example 1 in that the carbon fibers of the modified carbon fibers were first subjected to an etching treatment by using 0.5mol/L ammonium hydrogen carbonate as an electrolyte solution and having a current density of 0.15mA/cm 2 Carrying out continuous electrochemical oxidation treatment on the carbon fiber at the electrolysis temperature of 30 ℃ for 90-150 s; cleaning with circulating distilled water to remove residual electrolyte on the surface of the fiber; drying at 100 deg.C, gluing and collecting silk.
Example 10
The difference between the embodiment and the embodiment 1 is that the carbon fiber composite material further comprises epoxy resin, and the modified carbon fiber accounts for 55% of the volume fraction of each component, and the balance is a blend of the epoxy resin and urethane acrylate, and the epoxy resin accounts for 3% of the volume of the urethane acrylate.
Example 11
The difference between the embodiment and the embodiment 1 is that the carbon fiber composite material further comprises epoxy resin, and the modified carbon fiber accounts for 55% of the volume fraction of each component, and the balance is a blend of the epoxy resin and urethane acrylate, and the epoxy resin accounts for 5% of the volume of the urethane acrylate.
Example 12
The difference between the embodiment and the embodiment 1 is that the carbon fiber composite material further comprises epoxy resin, the modified carbon fiber accounts for 55% of the volume fraction of each component, the balance is a blend of the epoxy resin and urethane acrylate, and the epoxy resin accounts for 6% of the volume of the urethane acrylate.
Example 13
The carbon fiber composite material comprises 65% of polyurethane acrylate and modified carbon fiber, and the balance of the modified carbon fiber is polyurethane acrylate.
The preparation method of the polyurethane acrylate comprises the steps of adding polyisocyanate and polyether glycol into acetone, heating to 80 ℃, adding a tin catalyst, heating to 90 ℃, and stirring at constant temperature for 4 hours; cooling to 80 ℃, adding methyl methacrylate and butyl acrylate, continuing to react for 5 hours, adding a neutralizing agent, reacting for 40 minutes, adding deionized water, and stirring at high speed to obtain an emulsion with solid content of 70%. The mass ratio of acetone, polyisocyanate, polyether glycol, tin catalyst, methyl methacrylate, butyl acrylate and neutralizer is 5; the stirring speed was 3000r/min.
The preparation method of the modified carbon fiber comprises the following steps of 2 Dispersing the carbon fiber into an organic solvent, wherein the organic solvent is a mixed solution of absolute ethyl alcohol and a silane coupling agent, the volume ratio of the absolute ethyl alcohol to the silane coupling agent is 3Repeatedly filtering the water and the ethanol to obtain the grafted SiO 2 The carbon fiber of (1); carbon fiber SiO 2 The mass ratio of the organic solvent is 25; the ultrasonic treatment time is 40min, and the temperature is 120 ℃.
The preparation method of the carbon fiber composite material comprises the steps of carrying out ultrasonic stirring treatment on the polyurethane acrylate and the modified carbon fiber, wherein the ultrasonic time is 20min, and the temperature is 120 ℃.
Example 14
The carbon fiber composite material comprises polyurethane acrylate and modified carbon fibers, wherein the modified carbon fibers account for 35% by volume fraction, and the balance is the polyurethane acrylate.
The preparation method of the polyurethane acrylate comprises the steps of adding polyisocyanate and polyether glycol into acetone, heating to 50 ℃, adding a tin catalyst, heating to 70 ℃, and stirring at constant temperature for 3 hours; cooling to 50 ℃, adding methyl methacrylate and butyl acrylate, continuing to react for 2h, adding a neutralizing agent, reacting for 40min, adding deionized water, and stirring at high speed to obtain an emulsion with the solid content of 40%. The mass ratio of acetone, polyisocyanate, polyether glycol, tin catalyst, methyl methacrylate, butyl acrylate and neutralizer is 1; the stirring speed was 1000r/min.
The preparation method of the modified carbon fiber comprises the following steps of 2 Dispersing in an organic solvent, wherein the organic solvent is a mixed solution of absolute ethyl alcohol and a silane coupling agent, the volume ratio of the absolute ethyl alcohol to the silane coupling agent is 3 2 The carbon fiber of (3); carbon fiber SiO 2 The mass ratio of the organic solvent is 25; the ultrasonic treatment time is 25min, and the temperature is 80 ℃.
The preparation method of the carbon fiber composite material comprises the steps of carrying out ultrasonic stirring treatment on the polyurethane acrylate and the modified carbon fiber, wherein the ultrasonic time is 40min, and the temperature is 80 ℃.
Examples 15 to 26
The reinforced ultrahigh molecular weight polyethylene composition comprises, by weight, 100 parts of ultrahigh molecular weight polyethylene, 12 parts of low-density polyethylene, 40 parts of the carbon fiber composite material prepared in examples 1-12, 2 parts of a coupling agent, 1.5 parts of an antioxidant and 3 parts of a lubricant.
Figure BDA0002692595620000111
Example 27
This example differs from example 15 in that the coupling agent is vinyltributyl peroxy silane.
Example 28
The reinforced ultrahigh molecular weight polyethylene composition comprises, by weight, 100 parts of ultrahigh molecular weight polyethylene, 10 parts of low density polyethylene, 60 parts of the carbon fiber composite material prepared in example 13, 0.5 part of a coupling agent, 5 parts of an antioxidant and 2 parts of a lubricant.
Example 29
The reinforced ultra-high molecular weight polyethylene composition comprises, by weight, 100 parts of ultra-high molecular weight polyethylene, 20 parts of low density polyethylene, 10 parts of the carbon fiber composite material prepared in example 14, 3 parts of a coupling agent, 4 parts of an antioxidant and 4 parts of a lubricant.
Example 30
A method of making the reinforced ultrahigh molecular weight polyethylene composition of examples 15-29 comprising the steps of:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound; and (4) carrying out hot press molding and cold press molding on the rubber compound to obtain the enhanced ultra-high molecular weight polyethylene composition. The banburying temperature is 150 ℃ and the banburying time is 3min.
Example 31
A method of making the reinforced ultra high molecular weight polyethylene composition of examples 15-29, comprising the steps of:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound; and (4) carrying out hot press molding and cold press molding on the rubber compound to obtain the enhanced ultrahigh molecular weight polyethylene composition. The banburying temperature is 120 ℃ and the banburying time is 5min.
Example 32
A method of making the reinforced ultrahigh molecular weight polyethylene composition of examples 15-29 comprising the steps of:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound; and (4) carrying out hot press molding and cold press molding on the rubber compound to obtain the enhanced ultrahigh molecular weight polyethylene composition. The banburying temperature is 170 ℃ and the banburying time is 3min.
< comparative example >
Comparative example 1
This comparative example differs from example 15 in that the carbon fiber composite material was replaced with conventional carbon fiber.
Comparative example 2
This comparative example differs from example 15 in that the carbon fiber composite material was replaced with carbon fiber modified with a silane coupling agent.
Comparative example 3
The comparative example is different from example 15 in that the modified carbon fiber accounts for 75% of each component of the carbon fiber composite material in volume fraction, and the balance is urethane acrylate.
Comparative example 4
The comparative example is different from example 15 in that the modified carbon fiber accounts for 45% of each component of the carbon fiber composite material in volume fraction, and the balance is urethane acrylate.
Comparative example 5
This comparative example differs from example 15 in that the solids content of the urethane acrylate is 35%.
Comparative example 6
This comparative example differs from example 15 in that the solids content of the urethane acrylate was 85%.
Comparative example 7
The comparative example is different from example 15 in that in the preparation method of the modified carbon fiber, the carbon fiber SiO 2 The mass ratio of the organic solvent is 8.
Comparative example 8
The comparative example is different from example 15 in that in the preparation method of the modified carbon fiber, the carbon fiber SiO 2 The mass ratio of the organic solvent is 30.
< test example >
Examples 15 to 21,23 to 26 and comparative examples 1 to 8 were subjected to mechanical property tests as samples.
The results of the experiment are shown in table 1.
TABLE 1 mechanical Property test results for different samples
Figure BDA0002692595620000141
In summary, the blend product formed by polyethylene resin obtained by modifying carbon fiber with polyamide-acrylate has excellent mechanical properties of impact strength, tensile strength and bending.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The carbon fiber composite material is characterized by comprising a flexible body and modified carbon fibers dispersed in the flexible body, wherein the modified carbon fibers account for 50% -70% of the flexible body, and the balance of the flexible body; the flexible body comprises polyurethane acrylate, and the modified carbon fiber is inorganic nano particle grafted carbon fiber;
the preparation method of the modified carbon fiber comprises the following steps:
dispersing inorganic nanoparticles in an organic solvent, wherein the organic solvent is a mixed solution of absolute ethyl alcohol and a silane coupling agent, the volume ratio of the absolute ethyl alcohol to the silane coupling agent is 3-0.05-0.2, adding carbon fibers, carrying out ultrasonic oscillation treatment for reaction, and repeatedly carrying out suction filtration by using the absolute ethyl alcohol after the reaction to obtain the carbon fibers grafted with the inorganic nanoparticles; the mass ratio of the carbon fiber to the inorganic nanoparticles to the organic solvent is 10-30.
2. The carbon fiber composite material according to claim 1, wherein the flexible body further comprises epoxy resin, and the flexible body comprises 3-6% of epoxy resin and the balance of urethane acrylate according to volume fraction.
3. The carbon fiber composite material as claimed in claim 1 or 2, wherein the urethane acrylate is obtained by modifying polyurethane with methyl methacrylate and butyl acrylate.
4. The carbon fiber composite material as claimed in claim 1, wherein the ultrasonic treatment is carried out for 20 to 40min at a temperature of 80 to 120 ℃.
5. The carbon fiber composite material as claimed in claim 1, wherein the inorganic nanoparticles are TiO nanoparticles 2 、SiO 2 MgO, znO or silica sol.
6. A method for preparing a carbon fiber composite material as claimed in any one of claims 1 to 5, wherein the flexible body and the modified carbon fiber are subjected to ultrasonic agitation treatment, wherein the ultrasonic time is 40min to 60min, and the temperature is 60 ℃ to 80 ℃.
7. The reinforced ultrahigh molecular weight polyethylene composition is characterized by comprising 100 parts by weight of ultrahigh molecular weight polyethylene, 10-20 parts by weight of low density polyethylene, 10-60 parts by weight of the carbon fiber composite material as claimed in any one of claims 1-5, 0.5-3 parts by weight of coupling agent, 0.5-5 parts by weight of antioxidant and 2-4 parts by weight of lubricant.
8. The reinforced ultra high molecular weight polyethylene composition according to claim 7, wherein the coupling agent is an organosilicon peroxide coupling agent.
9. A process for the preparation of the reinforced ultra high molecular weight polyethylene composition according to claim 7 or 8, comprising the steps of:
adding the ultra-high molecular weight polyethylene, the low density polyethylene, the carbon fiber composite material, the coupling agent, the antioxidant and the lubricant into an internal mixer for internal mixing to obtain rubber compound;
and (4) carrying out hot press molding and cold press molding on the rubber compound to obtain the enhanced ultra-high molecular weight polyethylene composition.
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