CN112457548B - Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material - Google Patents
Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material Download PDFInfo
- Publication number
- CN112457548B CN112457548B CN202011353277.4A CN202011353277A CN112457548B CN 112457548 B CN112457548 B CN 112457548B CN 202011353277 A CN202011353277 A CN 202011353277A CN 112457548 B CN112457548 B CN 112457548B
- Authority
- CN
- China
- Prior art keywords
- graphene
- fibers
- composite material
- dispersion liquid
- coupling agent
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/18—Homopolymers or copolymers of nitriles
- C08J2433/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a preparation method of a graphene composite material with super wear resistance, flame retardance, high strength and mould resistance, and particularly relates to the field of preparation of graphene composite materials, aiming at solving the problem that the existing graphene composite material only can singly improve a certain performance, but the other performances are reduced, a coupling agent is added into ethanol to form a modification solution, and continuous fibers continuously pass through the modification solution to obtain fibers modified by the coupling agent; passing the coupling agent modified fibers through graphene dispersion liquid to obtain graphene-coated modified graphene fibers; adding a high polymer material into a single-screw extruder, adding a graphene oxide dispersion liquid into a high polymer material melt in a spraying mode after the high polymer material is completely plasticized, and compounding with 3-24 bundles of graphene-coated modified graphene fibers to form the graphene composite material. The material has excellent wear resistance, super-strong mechanical strength, flame retardance and anti-mildew performance, so that the performance of the composite material can be comprehensively improved by the graphene.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a graphene composite material with characteristics of super wear resistance, flame retardance, high strength and mold resistance.
Background
Graphene has attracted much attention as a novel carbon material since its discovery in 2004. The material is a quasi-two-dimensional crystal material which is composed of sp2 hybridized carbon atoms and has the thickness of only a single atomic layer or a plurality of single atomic layers, and has excellent performances of high light transmittance, electric conductivity, thermal conductivity, high specific surface area, high strength, flexibility and the like. Graphene has a thickness of up to 2600m2The ultrahigh specific surface area per gram is 100 times of that of steel, and the ultrahigh-strength composite material has good flexibility and extensibility, and theoretically can be added into a polymer matrix to enable the composite material to have higher strength, environmental stress cracking resistance and creep resistance; has better weather resistance (including ultraviolet resistance) and long-term thermal stability, more excellent wear resistance (smooth inner wall and small water flow resistance), more excellent low-temperature impact resistance and antibacterial and bacteriostatic effects.
The excellent mechanical property of the graphene is a basic condition for materials science, and some high polymer materials are particularly expected to improve wear resistance, lubrication, strength, flame retardance, mildew-resistant edges and the like due to the application occasions. For example, the compound has potential application to outer packaging of some equipment, special cable sheaths, sole materials of sports shoes and the like, the traditional formula needs to introduce various additives to achieve the effect, and the addition amount is very large, because too much additive affects the performance of the materials. The graphene has the comprehensive performance just like the above, but how to add and what kind of graphene is added is not sufficiently researched in the prior art, and after the graphene is added, some properties of the graphene are often improved and some properties of the graphene are often reduced, so that the simultaneous improvement is difficult to achieve.
CN 109627530A is prepared by screening out large-sheet-diameter (>10um) graphene, adding the graphene into a chloroprene colloid, drying, adding zinc oxide, magnesium oxide, stearic acid, an accelerator and the like, and milling on a mill to obtain a wear-resistant graphene composite material; however, in the method, graphene with a large sheet diameter is easy to curl, and the surface of the graphene is not treated, so that the interface bonding between the graphene and the chloroprene rubber is poor, and good dispersion is difficult to obtain by adopting common double-roll milling, so that the wear resistance is improved, but the other mechanical properties are poor.
The CN 107286559A utilizes graphene-TiO 2 suspension and polyether-ether-ketone suspension to mix, dry and mold to prepare the wear-resistant composite material, the method adopts a solution dispersion graphene mode to ensure that the agglomeration of graphene is small, but the graphene-TiO 2 is connected by physical action, and the interface combination effect of graphene and resin is still not solved.
CN 109161187A utilizes graphene oxide to add in the in-situ polymerization of nylon 6, through graphite alkene and caprolactam, has strengthened the wear resistance of PA 6. However, the graphene oxide in the application can cause the termination of ring-opening polymerization through the chemical reaction between the amino group or the carboxyl group in the caprolactam and the hydroxyl group and the carboxyl group on the graphene oxide, so that the molecular weight and the distribution of PA6 are affected, and the mechanical properties are difficult to repeat.
CN 108586718B prepares the composite material of graphene polyester thermoplastic elasticity by carrying out reduction and melt polymerization on graphene oxide and aliphatic high-crystallinity polyester prepolymer, graphene oxide and furan low-crystallinity polyester prepolymer and reduced graphene oxide/amorphous polyester prepolymer, and the preparation method adopts a solution method in-situ reduction mode, so that the electric conductivity, the heat conductivity and the tensile strength of the composite material are greatly improved, but the interface combination of the graphene and the polyester thermoplastic elasticity is still not solved, and the composite material is obtained by the non-covalent action.
CN111349305A utilizes graphene oxide to be aminated, then utilizes amino-terminated fluoropolyether or hydroxyl-terminated fluoropolyether to be modified, and then evenly mixes polyformaldehyde, antioxidant and coupled graphene oxide, and then melts and mixes to obtain the polyformaldehyde/graphene nanocomposite, wherein the impact resistance, tensile strength and wear resistance of the polyformaldehyde/graphene nanocomposite are improved. The application solves the dispersion of graphene in polyformaldehyde by utilizing modified dispersion, but the wear resistance and strength are improved to a limited extent, and the performances of flame retardance, mildew resistance and the like are not mentioned.
Disclosure of Invention
The invention aims to: the preparation method of the graphene composite material with super wear resistance, flame retardance, high strength and mould resistance is provided, so that the problem that the graphene composite material prepared in the prior art can only singly improve one property, and the other properties are reduced is solved.
The technical scheme adopted by the invention is as follows:
the preparation method of the graphene composite material with super wear resistance, flame retardance, high strength and mould resistance comprises the following steps:
step 1, adding a coupling agent into ethanol to form a modified solution, continuously passing continuous fibers through the modified solution, and rolling to obtain coupling agent modified fibers;
step 2, drying the coupling agent modified fibers through graphene dispersion liquid to obtain graphene coated modified graphene fibers; the drying temperature is 60-100 ℃, and the drying time is 0.1-1 s;
and 3, adding a high polymer material into a single-screw extruder, adding the graphene oxide dispersion liquid into a high polymer material melt in a spraying mode after the high polymer material is completely plasticized (at the rear end of the extruder), compounding the graphene oxide dispersion liquid with 3-24 bundles of graphene-coated modified graphene fibers, and forming the graphene composite material through a die.
According to the technical scheme, continuous fibers are modified by a coupling agent, the coupling agent is a cationic coupling agent, so that the fibers modified by the coupling agent are positively charged, graphene has negative charge performance due to a large pi bond formed by pi-pi conjugation, and the positive charge and the negative charge form strong bonding action through electrostatic action, so that the graphene is tightly coated on the surfaces of the fibers without agglomeration; the alkane coupling agent between the graphene and the fiber can generate a non-covalent effect with a high polymer material, so that the mechanical property of the fiber in a polyolefin non-polar high polymer is enhanced, for the other non-polar high polymer materials, a group on the graphene can generate a hydrogen bond with a polar molecule of the high polymer, so that the mechanical property of a matrix high polymer material is comprehensively improved, and the graphene and the fiber are compounded for enhancing the mechanical property of a composite material, so that a high-strength composite material is obtained; and the subsequent graphene dispersion liquid is introduced into the graphene at the rear end of the extrusion, so that agglomeration can be avoided, and the flame retardant, wear resistant and antibacterial properties of the material are greatly improved. Through the modification to graphite alkene to make its even distribution of graphite alkene on the fibre, form graphite alkene modified fiber, then crowd graphite alkene and continuous fiber altogether, thereby obtained graphite alkene/fibrous combined material, the material not only has excellent wear resistance, superstrong mechanical strength, fire-retardant and anti-mildew performance, makes graphite alkene can promote combined material's performance comprehensively, has solved the dispersion of graphite alkene in combined material, guarantees the dispersion homogeneity and the excellent interface bonding performance of graphite alkene.
Preferably, in step 1, the coupling agent includes any one of a cationic alkane coupling agent, gamma-aminopropyltriethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
Preferably, in step 1, the amount of the coupling agent added is 0.005-0.02 of the mass of ethanol.
Preferably, in step 1, the continuous fibers include one or more of polyamide fibers, polyester fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyethylene fibers, aromatic polyamide fibers, polyimide fibers, carbon fibers, graphitized fibers, polytetrafluoroethylene fibers, polyurethane fibers, and the like.
Preferably, in the step 2, the concentration of the graphene dispersion liquid is 0.05-2%.
Preferably, in step 2, the graphene in the graphene dispersion liquid includes graphene oxide and/or eigen-state graphene, the number of graphene oxide and eigen-state graphene layers is 1-5, the size of the sheet diameter is 10nm-1 μm, and when the graphene in the graphene dispersion liquid is graphene oxide and eigen-state graphene, the graphene oxide and the eigen-state graphene can be mixed in any proportion.
Preferably, in step 2, the solvent of the graphene dispersion liquid is any one of water, ethanol, and isopropanol.
Preferably, in step 3, the polymer material includes one or more of polyolefin, polystyrene, polyvinyl chloride, polyvinyl alcohol, acrylic, polyurethane, polyamide, polycarbonate, polyformaldehyde, polyphenylene oxide, polyester, polyimide, polysulfone, polyphenylene oxide, polyphenylene ester, polyarylate, polyether ether ketone and rubber.
Preferably, in step 3, the number of graphene oxide layers in the graphene oxide dispersion liquid is 1-5, the sheet diameter is 1-10 μm, and the C/O ratio is 2-3.
Preferably, in step 3, the concentration of the graphene oxide dispersion liquid is 0.05-2%, and the solvent of the graphene oxide dispersion liquid is one or more of water, ethanol or isopropanol.
Preferably, in step 3, the mass ratio of the graphene oxide in the resin is 0.01-1%.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the method, firstly, a coupling agent is used for modifying continuous fibers, the coupling agent is a cationic coupling agent, so that the fibers of the fibers modified by the coupling agent are positively charged, graphene has negative charge performance due to a large pi bond formed by pi-pi conjugation, and the positive charge and the negative charge form strong bonding action through electrostatic action, so that the graphene is tightly coated on the surfaces of the fibers without agglomeration;
2. the alkane coupling agent (modifier) between the graphene and the fiber can generate a non-covalent effect with a high polymer material, so that the mechanical property of the fiber in a polyolefin non-polar high polymer is enhanced, and for other non-polar high polymer materials, a group on the graphene can generate a hydrogen bond with a polar molecule of the high polymer, so that the mechanical property of a matrix high polymer material is comprehensively improved;
3. and the subsequent graphene dispersion liquid is introduced into the graphene at the rear end of the extrusion, so that agglomeration can be avoided, and the flame retardant, wear resistant and antibacterial properties of the material are greatly improved.
Drawings
FIG. 1 is an SEM image of an aromatic polyamide fiber;
fig. 2 is an SEM topography of the graphene modified fiber composite material prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Fiber pretreatment: adding 1g of cationic alkane coupling agent into 200g of 95% ethanol to form a modification solution, continuously passing polyamide fibers (continuous fibers) through the modification solution, and rolling to obtain fibers modified by the cationic alkane coupling agent;
preparing a graphene/fiber composite material: drying the fiber modified by the cationic alkane coupling agent through 0.05% of single-layer graphene oxide dispersion liquid with the sheet diameter of 10nm at the drying temperature of 60 ℃ for 1s to obtain graphene-coated modified graphene fiber;
preparing a graphene modified fiber composite material: adding 10kg of polyolefin into a single-screw extruder, adding a graphene oxide dispersion liquid (solvent is water) with the sheet diameter of 1 micrometer, the carbon-oxygen ratio of 2 and the average layer number of 1 layer into a polyolefin melt in a spraying mode after the polyolefin is completely plasticized, wherein the concentration of the graphene oxide dispersion liquid is 0.07%, the addition amount of the graphene is 0.01% of the mass of the polyolefin, compounding the graphene oxide dispersion liquid with 10 bundles of graphene-coated modified graphene fibers, and forming a graphene composite material through a mold.
Example 2
Fiber pretreatment: adding 1g of gamma-aminopropyltriethoxysilane into 100g of 95% ethanol to form a modification solution, continuously passing aromatic polyamide fibers (continuous fibers) through the modification solution, and rolling to obtain gamma-aminopropyltriethoxysilane coupling agent modified fibers;
preparing a graphene/fiber composite material: drying the fiber modified by the gamma-aminopropyltriethoxysilane coupling agent through 3 layers of graphene oxide dispersion liquid with the sheet diameter of 100nm and the concentration of 1%, wherein the drying temperature is 80 ℃, and the drying time is 0.5s, so as to obtain graphene coated and modified graphene fiber;
preparing a graphene modified fiber composite material: adding 20kg of polyurethane (elastomer material) into a single-screw extruder, then after the polyurethane is completely plasticized, adding a graphene oxide dispersion liquid (solvent is water) with the sheet diameter of 3 microns, the carbon-oxygen ratio of 2.2 and the average number of layers of 3 into a polyurethane melt in a spraying mode, wherein the concentration of the graphene oxide dispersion liquid is 0.07%, the addition amount of graphene is 0.5% of the mass of the polyurethane, compounding the graphene oxide dispersion liquid with 12 bundles of graphene-coated modified graphene fibers, and passing through a die to form the graphene composite material.
Example 3
Fiber pretreatment: adding 4g of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane into 200g of 95% ethanol to form a modified solution, continuously passing polyester fibers through the modified solution, and rolling to obtain fibers modified by the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent;
preparing a graphene/fiber composite material: the fiber modified by the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent is dried by 4 layers of graphene oxide dispersion liquid with the sheet diameter of 1 mu m and the concentration of 2 percent, the drying temperature is 100 ℃, and the drying time is 0.1s, so that the graphene fiber coated and modified by graphene is obtained;
preparing a graphene modified fiber composite material: adding 30kg of polyamide into a single-screw extruder, then after the polyamide is completely plasticized, adding a graphene oxide dispersion liquid (the solvent is ethanol) with the sheet diameter of 10 microns, the carbon-oxygen ratio of 3 and the average layer number of 4 layers into a polyamide melt in a spraying mode, wherein the concentration of the graphene oxide dispersion liquid is 1%, the addition amount of graphene is 1% of the mass of polyurethane, then compounding with 16 bundles of graphene-coated modified graphene fibers, and passing through a die to form the graphene composite material.
Example 4
Fiber pretreatment: adding 1g of gamma-aminopropyltriethoxysilane into 100g of 95% ethanol to form a modifying solution, continuously passing polyvinyl chloride fibers (continuous fibers) through the modifying solution, and rolling to obtain gamma-aminopropyltriethoxysilane coupling agent modified fibers;
preparing a graphene/fiber composite material: drying the fiber modified by the gamma-aminopropyltriethoxysilane coupling agent through 1% of monolayer graphene oxide with the sheet diameter of 100nm and monolayer eigenstate graphene dispersion liquid with the sheet diameter of 100nm, wherein the drying temperature is 80 ℃, and the drying time is 0.5s, so as to obtain graphene coated and modified graphene fiber;
preparing a graphene modified fiber composite material: adding 10kg of polyimide (elastomer material) into a single-screw extruder, then after the polyimide is completely plasticized, adding a graphene oxide dispersion liquid (the solvent is propanol) with the sheet diameter of 3 microns, the carbon-oxygen ratio of 2.2 and the average layer number of 3 layers into a polyimide melt in a spraying mode, wherein the concentration of the graphene oxide dispersion liquid is 0.07%, the addition amount of graphene is 0.5% of the mass of polyurethane, compounding the graphene oxide dispersion liquid with 10 bundles of graphene-coated modified graphene fibers, and passing through a die to form the graphene composite material.
Example 5
Fiber pretreatment: adding 1g of cationic alkane coupling agent into 100g of 95% ethanol to form a modifying solution, continuously passing polyvinyl chloride fibers (continuous fibers) through the modifying solution, and rolling to obtain fibers modified by the cationic alkane coupling agent;
preparing a graphene/fiber composite material: drying the fiber modified by the cationic alkane coupling agent through a single-layer graphene oxide dispersion liquid with the sheet diameter of 300nm and the concentration of 1%, wherein the drying temperature is 80 ℃, and the drying time is 0.5s, so as to obtain graphene-coated modified graphene fiber;
preparing a graphene modified fiber composite material: adding 10kg of polyarylate (elastomer material) into a single-screw extruder, after the polyarylate is completely plasticized, adding a graphene oxide dispersion liquid (solvent is water) with the sheet diameter of 3 micrometers, the carbon-oxygen ratio of 2.2 and the average number of layers of 3 into a polyarylate melt in a spraying mode, wherein the concentration of the graphene oxide dispersion liquid is 0.07%, the addition amount of graphene is 0.5% of the mass of polyurethane, compounding the graphene oxide dispersion liquid with 18 bundles of graphene-coated modified graphene fibers, and passing through a die to form the graphene composite material.
Example 6
Fiber pretreatment: adding 1g of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane into 100g of 95% ethanol to form a modified solution, continuously passing polyacrylonitrile fibers (continuous fibers) through the modified solution, and rolling to obtain fibers modified by the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent;
preparing a graphene/fiber composite material: drying the fiber modified by the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent through a single-layer graphene oxide dispersion liquid with the sheet diameter of 500nm and the concentration of 1%, wherein the drying temperature is 80 ℃, and the drying time is 0.5s, so as to obtain graphene fiber coated and modified by graphene;
preparing a graphene modified fiber composite material: adding 10kg of acrylic acid (elastomer material) into a single-screw extruder, then after the acrylic acid is completely plasticized, adding a graphene oxide dispersion liquid (solvent is water) with the sheet diameter of 3 microns, the carbon-oxygen ratio of 2.2 and the average number of layers of 3 into an acrylic acid melt in a spraying mode, wherein the concentration of the graphene oxide dispersion liquid is 1%, the addition amount of graphene is 0.5% of the mass of polyurethane, then compounding with 20 bundles of graphene-coated modified graphene fibers, and passing through a die to form the graphene composite material.
The graphene modified fiber composite materials prepared in examples 1 to 6 were made into special cables, and the test results are shown in table 1:
table 1 test results of the graphene modified fiber composite materials of examples 1 to 6 after being made into special cables
Wherein, the wear-resisting test condition of cable sample is: tensile load 4.5N, scraping length 5cm, 60 times/min. The cable samples should be subjected to a number of cycles of abrasion and rubbing, and after testing, visual inspection is performed and any inner layer of the jacket is left uncovered as failure.
Mold test selection reference GJB150.10A, strain selection group 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the graphene composite material with super wear resistance, flame retardance, high strength and mould resistance is characterized by comprising the following steps:
step 1, adding a coupling agent into ethanol to form a modified solution, continuously passing continuous fibers through the modified solution, and rolling to obtain coupling agent modified fibers; the coupling agent comprises any one of cationic alkane coupling agent, gamma-aminopropyltriethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane;
step 2, drying the coupling agent modified fibers through graphene dispersion liquid to obtain graphene coated modified graphene fibers;
and 3, adding a high polymer material into a single-screw extruder, adding the graphene oxide dispersion liquid into a high polymer material melt in a spraying mode after the high polymer material is completely plasticized, compounding the graphene oxide dispersion liquid with 3-24 bundles of graphene-coated modified graphene fibers, and forming the graphene composite material through a die.
2. The preparation method of the graphene composite material with the characteristics of super wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 1, the addition amount of the coupling agent is 0.005-0.02 times of the mass of the ethanol.
3. The method for preparing the graphene composite material with ultra wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 1, the continuous fibers comprise one or more of polyamide fibers, polyester fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyethylene fibers, polyimide fibers, carbon fibers, graphitized fibers, polytetrafluoroethylene fibers, polyurethane fibers and the like.
4. The preparation method of the graphene composite material with the characteristics of super wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 2, the concentration of the graphene dispersion liquid is 0.05-2%.
5. The method for preparing the graphene composite material with the characteristics of super wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 2, the graphene in the graphene dispersion liquid comprises graphene oxide and/or eigenstate graphene, the number of layers is 1-5, and the size of the sheet diameter is 10nm-1 μm.
6. The method for preparing the graphene composite material with ultra wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 3, the high polymer material comprises one or more of polyolefin, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyamide, polycarbonate, polyformaldehyde, polyphenyl ether, polyester, polyimide, polysulfone, polyphenyl ester, polyarylate and polyether ether ketone.
7. The method for preparing the graphene composite material with ultra wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 3, the high polymer material comprises rubber.
8. The preparation method of the graphene composite material with the characteristics of super wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 3, the number of graphene oxide layers in the graphene oxide dispersion liquid is 1-5, the sheet diameter is 1-10 μm, and the C/O is 2-3.
9. The method for preparing the graphene composite material with ultra wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 3, the concentration of the graphene oxide dispersion liquid is 0.05-2%, and the solvent of the graphene oxide dispersion liquid is one or more of water, ethanol or isopropanol.
10. The preparation method of the graphene composite material with the characteristics of super wear resistance, flame retardance, high strength and mold resistance according to claim 1, wherein in the step 3, the mass ratio of graphene oxide in the resin is 0.01-1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011353277.4A CN112457548B (en) | 2020-11-26 | 2020-11-26 | Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011353277.4A CN112457548B (en) | 2020-11-26 | 2020-11-26 | Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112457548A CN112457548A (en) | 2021-03-09 |
| CN112457548B true CN112457548B (en) | 2021-08-31 |
Family
ID=74808914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011353277.4A Active CN112457548B (en) | 2020-11-26 | 2020-11-26 | Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457548B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395172B (en) * | 2022-01-20 | 2023-12-01 | 北京石墨烯技术研究院有限公司 | Polytetrafluoroethylene modified filler, modified polytetrafluoroethylene composite material, preparation method and application |
| CN114479391B (en) * | 2022-01-26 | 2023-06-23 | 安徽理工大学 | Preparation method of graphene oxide/bisphenol-A type polyarylate composite material |
| CN114479390B (en) * | 2022-01-26 | 2023-06-23 | 安徽理工大学 | Preparation method of graphene oxide/phenol red type polyarylester composite material |
| CN114350142A (en) * | 2022-01-26 | 2022-04-15 | 福州大学 | Reinforced nylon 12 composite material for MJR3D printed coconut shell fiber surface grafted graphene oxide and preparation method thereof |
| CN115491784A (en) * | 2022-08-24 | 2022-12-20 | 凯盛石墨碳材料有限公司 | Preparation method of graphene/carbon fiber/polypropylene fiber with excellent conductivity |
| CN116041798A (en) * | 2022-12-23 | 2023-05-02 | 海南中之林仿生科技有限公司 | Fiber reinforced thermoplastic starch plate and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262953B (en) * | 2014-08-21 | 2016-06-29 | 巨石集团有限公司 | A kind of Graphene coated glass fiber strengthens polymer matrix composites and preparation method |
| CN105802142A (en) * | 2016-05-06 | 2016-07-27 | 金思宇 | Graphene modified fiber reinforced resin-based composite material and preparation method thereof |
| CN105778464B (en) * | 2016-05-14 | 2018-01-26 | 湖北运来塑胶科技有限公司 | A kind of graphene/glass fiber reinforced polycarbonate composite and preparation method thereof |
| CN105802019B (en) * | 2016-05-14 | 2018-10-16 | 湖北运来塑胶科技有限公司 | A kind of graphene/glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN106115668A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | The process for dispersing of a kind of Graphene and graphene composite material |
| CN109610027B (en) * | 2018-01-08 | 2021-01-19 | 江苏恒辉安防股份有限公司 | Graphene composite ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN108610559B (en) * | 2018-04-13 | 2021-06-15 | 武汉金发科技有限公司 | Graphene modified polypropylene composite material and preparation method thereof |
-
2020
- 2020-11-26 CN CN202011353277.4A patent/CN112457548B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112457548A (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112457548B (en) | Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material | |
| Prashantha et al. | Multi-walled carbon nanotube filled polypropylene nanocomposites based on masterbatch route: Improvement of dispersion and mechanical properties through PP-g-MA addition | |
| Ren et al. | Influence of functional graphene as filler on the tribological behaviors of Nomex fabric/phenolic composite | |
| Fu et al. | Mechanical properties of polypropylene composites reinforced by hydrolyzed and microfibrillated Kevlar fibers | |
| Chen et al. | The effect of double grafted interface layer on the properties of carbon fiber reinforced polyamide 66 composites | |
| Wu et al. | Facile and simple fabrication of strong, transparent and flexible aramid nanofibers/bacterial cellulose nanocomposite membranes | |
| Yang et al. | Electrospun carbon nanofibers and their reinforced composites: Preparation, modification, applications, and perspectives | |
| CN102924910B (en) | Method of preparing high-performance glass-fiber reinforced polyamide conductive composite | |
| Aouat et al. | Morphological, mechanical, and thermal characterization of poly (lactic acid)/cellulose multifilament fibers prepared by melt spinning | |
| CN111732778B (en) | Preparation method of high-thermal-conductivity composite material | |
| Dai et al. | Mechanical properties of carbon nanotubes-polymer composites | |
| Mishra et al. | Manipulation of thermo-mechanical, morphological and electrical properties of PP/PET polymer blend using MWCNT as nano compatibilizer: A comprehensive study of hybrid nanocomposites | |
| Yin et al. | Surface construction of ANF/CNT onto aramid fibers to enhance interfacial adhesion and provide real-time monitoring of deformation | |
| Yang et al. | Enhanced mechanical and tribological properties of Kevlar/PTFE‐phenolic composites by improving interfacial properties by aramid nanofibers | |
| Wu et al. | Preparation and characterization of polyamide composites with modified graphite powders | |
| Cheng et al. | Surface modification of halloysite nanotubes grafted by dodecylamine and their application in reinforcing polytetrafluoroethylene | |
| Ma et al. | Modified treatment for carbonized cellulose nanofiber application in composites | |
| CN110229473B (en) | PET (polyethylene terephthalate) nano composite material and preparation method thereof | |
| Mathur et al. | Properties of PMMA/carbon nanotubes nanocomposites | |
| Kim et al. | Synergistic mechanical reinforcement of woven carbon fiber/polypropylene composites using plasma treatment and nanoclay | |
| JP2015535869A (en) | Carbon nanomaterial-containing resin composition and plastic molded article | |
| CN112204081A (en) | Method for coating fibers containing polar moieties | |
| Tawiah et al. | Tribology of hybrid nanofiller/polymer nanocomposites | |
| Liu et al. | Enhanced mechanical properties, thermal behavior and foaming ability of PP‐g‐MAH modified PP/BF composites | |
| CN114836035A (en) | Modified polyphenylene sulfide and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 618000 office building, No. 213, Qilianshan Road, Jingyang District, Deyang City, Sichuan Province Patentee after: Sichuan 6912 Communication Technology Co.,Ltd. Address before: 618000, 213 Qilianshan Road, Jingyang District, Deyang City, Sichuan Province Patentee before: SICHUAN LIUJIU YIER TECHNOLOGY Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of graphene composite materials with super wear resistance, flame retardancy, high strength, and mold resistance Effective date of registration: 20230412 Granted publication date: 20210831 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Sichuan 6912 Communication Technology Co.,Ltd. Registration number: Y2023980037853 |