CN111285999A - Graphene polyurethane composite plastic for sports equipment and preparation method thereof - Google Patents
Graphene polyurethane composite plastic for sports equipment and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08K3/041—Carbon nanotubes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention belongs to the technical field of sports equipment, and provides graphene polyurethane composite plastic for the sports equipment and a preparation method thereof. According to the method, a carbon nano tube sequentially passes through a coupling agent and a mixed solution containing graphene and toluene diisocyanate in a spray pipe, and enters a receiving device containing hydroxyl-terminated polytetrahydrofuran and a catalyst to react to generate the polyurethane composite plastic with uniformly dispersed graphene. Compared with the traditional method, the composite plastic prepared by the invention has the advantages that the graphene is uniformly dispersed in the matrix, the interface bonding capability of the graphene, the carbon nano tube and the polyurethane matrix is improved, the tensile strength of the composite material is obviously improved, the preparation process is simple, the cost is lower, the performance is excellent, and the composite plastic can be widely used for light sports equipment.
Description
Technical Field
The invention belongs to the technical field of sports equipment, and provides graphene polyurethane composite plastic for the sports equipment and a preparation method thereof.
Background
With the improvement of living standard of people, the sport and fitness become more and more concerned, and light and high-strength sports equipment is widely popularized. The carbon fiber is a novel fiber material of high-strength and high-modulus fiber with the carbon content of more than 95 percent. The accepted sports equipment with superior performance is carbon fiber composite material, and compared with the traditional metal material and composite material, the carbon fiber composite material has the characteristics of light weight, high strength and fatigue resistance. The density of the carbon fiber composite material is only 1/5 of steel and 3/5 of aluminum, but the strength of the carbon fiber composite material is 5 times that of the steel and 4 times that of the aluminum, and the carbon fiber composite material has excellent performance, but the production process is complex and the cost is high, so that the carbon fiber composite material is not popularized in a large quantity.
Graphene is favored in the field of new materials due to its unique two-dimensional characteristics, large specific surface area, excellent electrical conductivity, thermal conductivity, and high strength. Graphene (GO) and graphene have certain commonality, and the graphene modified composite material has excellent performance, is widely applied to the fields of electronics, machinery, new energy and the like, and is an ideal modified material of a sports article composite material.
At present, sports goods technology at home and abroad, particularly, the technology has achieved certain effect on the aspect of adding modified sports goods such as carbon fiber, graphene and the like. Wherein the vengean invents a net thread for a badminton racket (Chinese invention patent application No. 201610766338.7), which is prepared from the following raw materials: polyhexamethylene adipamide, poly [ imino (1-oxo-1, 12-dodecylene) ], polymers of dodecanoic acid with 1, 6-hexanediamine, carbon fiber, graphene, modified polyalkene fiber, hydroxypropyl cellulose, diatomaceous earth, sodium 2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, dilauryl thiodipropionate, diphenyl phosphate, 3- (2-aminoethylamine) propyl methyldimethoxysilane; the net thread for the badminton racket has excellent strength and better elasticity compared with the traditional nylon net thread by reasonable proportioning and combined action of the raw materials. In addition, Jinyun et al invented a titanium metal reinforced carbon fiber badminton racket composite material (Chinese patent application No. 201510455348.4), which comprises the following raw materials: carbon fiber, nano titanium dioxide, acrylate resin, perchloroethylene resin, ethyl cellulose, polyamide fiber, acrylonitrile, nano alumina, trihydroxyethyl methyl quaternary ammonium methyl sulfate, a foaming agent, a coupling agent and a stabilizing agent; the composite material takes carbon fiber as a main body, and titanium dioxide and resin materials are added, so that the composite material can be popularized and used.
Therefore, in the prior art, the composite materials such as carbon fibers and the like used for sports goods such as badminton rackets and the like have the defects of complicated preparation process, higher cost, poor tensile strength and the like, and the traditional technical method for adding the modified fillers such as graphene and the like has poor modification effect and is difficult to popularize and apply due to poor interface bonding property and uneven dispersion of the fillers and a matrix.
Disclosure of Invention
Aiming at the situation, the graphene polyurethane composite plastic for sports equipment and the preparation method thereof are provided, so that the tensile strength of the composite plastic can be effectively improved, the preparation process is simple, and the cost is low.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of graphene polyurethane composite plastic for sports equipment comprises the following steps of enabling carbon nano tubes to sequentially pass through a coupling agent and a mixed solution containing graphene and toluene diisocyanate in a spray pipe, enabling the mixture to enter a receiving device containing hydroxyl-terminated polytetrahydrofuran and a catalyst, and reacting to generate the uniformly dispersed graphene polyurethane composite plastic, wherein the preparation method comprises the following specific steps:
(1) adding graphene into a xylene solvent, performing ultrasonic dispersion, adding toluene diisocyanate, and performing magnetic stirring until the mixture is uniformly mixed to obtain a mixed solution;
(2) dividing a spray pipe of a spray dryer into three sections for feeding, wherein the first section is a carbon nano tube, the second section is a KH550 coupling agent, the third section is the mixed solution prepared in the step (1), and a dimethylbenzene solution of hydroxyl-terminated polytetrahydrofuran and a catalyst are added into a receiving device;
(3) the carbon nano tubes in the atomizer rapidly penetrate through the coupling agent layer under certain pressure and then enter the mixed liquid layer, the liquid is atomized into mixed particles, and the mixed particles fall into a receiving device to participate in reaction, so that the graphene/polyurethane composite plastic is prepared.
Preferably, the raw materials in the step (1) comprise, by weight, 2-3 parts of graphene, 62-68 parts of xylene and 30-35 parts of toluene diisocyanate.
Preferably, the ultrasonic power of the ultrasonic dispersion in the step (1) is 150-200W, and the time is 1.5-2.5 h.
Preferably, the rotating speed of the magnetic stirring in the step (1) is 200-300 r/min, and the time is 3-5 h.
Preferably, in the spray pipe in the step (2), 2-3 parts by weight of carbon nanotubes, 1-2 parts by weight of KH550 coupling agent and 95-97 parts by weight of mixed solution are used.
Preferably, in the receiving device in the step (2), the hydroxyl-terminated polytetrahydrofuran is 20 to 32 parts by weight, the xylene is 64 to 78 parts by weight, and the catalyst is 2 to 4 parts by weight.
Preferably, the catalyst in step (2) is at least one of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine and N, N-dimethylbenzylamine.
Preferably, the atomization pressure in the step (3) is 100-150 bar, and the advancing speed of the carbon nano tube is 2-3 m/s.
Preferably, the particle size of the atomized particles of the mixed liquid in the step (3) is 20 to 50 μm.
Graphene is favored in the field of new materials due to its unique two-dimensional characteristics, large specific surface area, excellent electrical conductivity, thermal conductivity, and high strength. The graphene and the graphene have certain commonality, and the composite material modified by the graphene is an ideal modified material of the composite material of sports goods. According to the invention, a modified spray drying tube device is adopted to coat the coupling agent KH550 on the surface layer of the carbon nano tube, and then the coupling agent KH550 is connected with the prepared graphene/toluene diisocyanate mixed solution to form spray particles, the toluene diisocyanate in the particles is reacted with the hydroxyl-terminated polytetrahydrofuran in the receiving device to generate polyurethane, and the graphene is uniformly coated in the polyurethane, so that the comprehensive performance of the composite material is greatly improved.
The invention also provides the graphene polyurethane composite plastic for sports equipment, which is prepared by the preparation method.
The composite plastic is prepared by dispersing graphene into a xylene solvent, performing ultrasonic dispersion, adding toluene diisocyanate, stirring to form a mixed solution, dividing a spray pipe of a spray dryer into three sections, wherein the first section is a carbon nano tube, the second section is a KH550 coupling agent, the third section is a prepared mixed solution, a xylene solution of hydroxyl-terminated polytetrahydrofuran and a catalyst are filled in a receiving device, the carbon nano tube in an atomizer rapidly penetrates through the second section of coupling agent layer under a certain pressure, then the carbon nano tube enters the third section of mixed solution layer, and the liquid is atomized into mixed particles which fall into the receiving device to participate in reaction.
The invention provides graphene polyurethane composite plastic for sports equipment and a preparation method thereof, and compared with the prior art, the graphene polyurethane composite plastic has the outstanding characteristics and excellent effects that:
1. the graphene/polyurethane composite plastic prepared by the invention enables graphene to be uniformly dispersed, not only improves the strength, but also endows good flexibility, and can be widely used for sports equipment.
2. According to the preparation method disclosed by the invention, the carbon nano tubes in the spray pipe penetrate through the KH550 layer of the coupling agent to form effective connection with the graphene, so that the graphene can be effectively promoted to be uniformly dispersed in the matrix, the interface bonding capability of the graphene, the carbon nano tubes and the polyurethane matrix can be improved, and the tensile strength of the composite material is obviously improved.
3. The preparation method disclosed by the invention has the advantages that the addition amount of the graphene and the carbon nano tube is small, the cost of the composite material is effectively reduced compared with that of a large amount of carbon fiber filling, the preparation process is simple, and the popularization, the production and the application are convenient.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Adding 2kg of graphene into 65kg of xylene solvent, ultrasonically dispersing for 2h under the power of 170W, then adding 33kg of toluene diisocyanate, magnetically stirring for 4h at the rotating speed of 260r/min, and uniformly mixing to obtain a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 2kg of carbon nano-tubes, the second section is 2kg of KH550 coupling agent, the third section is 96kg of mixed liquor, and 27kg of dimethylbenzene solution of hydroxyl-terminated polytetrahydrofuran and 3kg of N, N-dimethylcyclohexylamine are added into a receiving device; and finally, under the pressure of 130bar, enabling the carbon nanotubes in the atomizer to penetrate through the coupling agent layer at the speed of 2.5m/s, then enabling the carbon nanotubes to enter the mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 30 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to obtain the graphene/polyurethane composite plastic.
The test method comprises the following steps:
tensile strength: a tensile strength test is carried out according to GB/T1040.5-2008 standard, a B-type standard sample with the length of 250mm, the width of 25mm and the thickness of 2mm is prepared from the composite material prepared by the invention, a tensile testing machine is used for testing, the test speed is 50mm/min at normal temperature and normal pressure, the measurement is carried out for 5 times, and the average value of the tensile strength is calculated.
The data obtained are shown in Table 1.
Example 2
Adding 2kg of graphene into 68kg of xylene solvent, ultrasonically dispersing for 2.5h under the power of 150W, then adding 30kg of toluene diisocyanate, magnetically stirring for 5h at the rotating speed of 200r/min, and uniformly mixing to obtain a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 2kg of carbon nano-tubes, the second section is 1kg of KH550 coupling agent, the third section is 97kg of mixed solution, and 20kg of xylene solution of hydroxyl-terminated polytetrahydrofuran and 2kg of bis (2-dimethylaminoethyl) ether are added into a receiving device; and finally, under the pressure of 100bar, enabling the carbon nanotubes in the atomizer to penetrate through a coupling agent layer at the speed of 2m/s, then enabling the carbon nanotubes to enter a mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 20 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to prepare the graphene/polyurethane composite plastic.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 3
Adding 3kg of graphene into 62kg of xylene solvent, ultrasonically dispersing for 1.5h under the power of 200W, then adding 35kg of toluene diisocyanate, magnetically stirring for 3h at the rotating speed of 300r/min, and uniformly mixing to obtain a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 3kg of carbon nano-tubes, the second section is 2kg of KH550 coupling agent, the third section is 95kg of mixed solution, and 32kg of xylene solution of hydroxyl-terminated polytetrahydrofuran and 4kg of N, N, N ', N' -tetramethylalkylenediamine are added into a receiving device; and finally, under the pressure of 150bar, enabling the carbon nanotubes in the atomizer to penetrate through a coupling agent layer at the speed of 3m/s, then enabling the carbon nanotubes to enter a mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 50 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to prepare the graphene/polyurethane composite plastic.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 4
Adding 2kg of graphene into 66kg of xylene solvent, ultrasonically dispersing for 2.5h under the power of 160W, then adding 32kg of toluene diisocyanate, and magnetically stirring at the rotating speed of 220r/min for 4.5h to uniformly mix to obtain a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 2kg of carbon nano-tubes, the second section is 1kg of KH550 coupling agent, the third section is 97kg of mixed liquor, and 23kg of xylene solution of hydroxyl-terminated polytetrahydrofuran and 3kg of triethylamine are added into a receiving device; and finally, under the pressure of 110bar, enabling the carbon nanotubes in the atomizer to penetrate through a coupling agent layer at the speed of 2m/s, then enabling the carbon nanotubes to enter a mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 30 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to prepare the graphene/polyurethane composite plastic.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 5
Adding 3kg of graphene into 66kg of xylene solvent, ultrasonically dispersing for 1.5h under the power of 190W, then adding 31kg of toluene diisocyanate, and magnetically stirring for 3.5h at the rotating speed of 280r/min to uniformly mix to prepare a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 3kg of carbon nano-tubes, the second section is 1kg of KH550 coupling agent, the third section is 96g of mixed liquor, and 30kg of dimethylbenzene solution of hydroxyl-terminated polytetrahydrofuran and 4kg of N, N-dimethylbenzylamine are added into a receiving device; and finally, under the pressure of 140bar, enabling the carbon nanotubes in the atomizer to penetrate through a coupling agent layer at the speed of 2m/s, then enabling the carbon nanotubes to enter a mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 40 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to prepare the graphene/polyurethane composite plastic.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 6
Adding 2kg of graphene into 65kg of xylene solvent, ultrasonically dispersing for 2 under the power of 180W, then adding 33kg of toluene diisocyanate, magnetically stirring at the rotating speed of 250r/min for 4 hours, and uniformly mixing to obtain a mixed solution; dividing a spray pipe of a spray dryer into three sections, wherein the first section is 2kg of carbon nano-tubes, the second section is 2kg of KH550 coupling agent, the third section is 96kg of mixed liquor, and 26kg of dimethylbenzene solution of hydroxyl-terminated polytetrahydrofuran and 3kg of N, N-dimethylcyclohexylamine are added into a receiving device; and finally, under the pressure of 125bar, enabling the carbon nanotubes in the atomizer to penetrate through the coupling agent layer at the speed of 2.5m/s, then enabling the carbon nanotubes to enter the mixed liquid layer, atomizing the liquid into mixed particles with the average particle size of 35 microns, and enabling the mixed particles to fall into a receiving device for participating in reaction to prepare the graphene/polyurethane composite plastic.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Comparative example 1
In the preparation process of the composite plastic, no graphene is added, and other preparation conditions are consistent with those of example 6.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Table 1:
| performance index | Elongation at Break (%) | Tensile Strength (MPa) | Modulus of elasticity (MPa) |
| Example 1 | 1400 | 7.5 | 25 |
| Example 2 | 1500 | 6.2 | 22 |
| Example 3 | 1200 | 6.2 | 24 |
| Example 4 | 1250 | 7.1 | 21 |
| Example 5 | 1300 | 6.4 | 23 |
| Example 6 | 1450 | 6.5 | 22 |
| Comparative example 1 | 850 | 5.1 | 11.0 |
Claims (10)
1. A preparation method of graphene polyurethane composite plastic for sports equipment is characterized in that a carbon nano tube sequentially passes through a coupling agent and a mixed solution containing graphene and toluene diisocyanate in a spray pipe and enters a receiving device containing hydroxyl-terminated polytetrahydrofuran and a catalyst to react to generate the uniformly dispersed graphene polyurethane composite plastic, and the preparation method comprises the following specific steps:
(1) adding graphene into a xylene solvent, performing ultrasonic dispersion, adding toluene diisocyanate, and performing magnetic stirring until the mixture is uniformly mixed to obtain a mixed solution;
(2) dividing a spray pipe of a spray dryer into three sections of feed inlets, wherein the first section is a carbon nano tube, the second section is a KH550 coupling agent, the third section is the mixed solution prepared in the step (1), and a dimethylbenzene solution of hydroxyl-terminated polytetrahydrofuran and a catalyst are added into a receiving device;
(3) the carbon nano tubes in the atomizer rapidly penetrate through the coupling agent layer under certain pressure and then enter the mixed liquid layer, the liquid is atomized into mixed particles, and the mixed particles fall into a receiving device to participate in reaction, so that the graphene/polyurethane composite plastic is prepared.
2. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: the raw materials in the step (1) comprise, by weight, 2-3 parts of graphene, 62-68 parts of xylene and 30-35 parts of toluene diisocyanate.
3. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: the ultrasonic power of the ultrasonic dispersion in the step (1) is 150-200W, and the time is 1.5-2.5 h.
4. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: the rotating speed of the magnetic stirring in the step (1) is 200-300 r/min, and the time is 3-5 h.
5. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: in the spray pipe in the step (2), 2-3 parts by weight of carbon nano tubes, 1-2 parts by weight of KH550 coupling agent and 95-97 parts by weight of mixed liquid are added.
6. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: in the receiving device in the step (2), 20-32 parts by weight of hydroxyl-terminated polytetrahydrofuran, 64-78 parts by weight of xylene and 2-4 parts by weight of a catalyst are used.
7. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: the catalyst in the step (2) is at least one of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine and N, N-dimethylbenzylamine.
8. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: and (3) atomizing at 100-150 bar, wherein the advancing speed of the carbon nano tube is 2-3 m/s.
9. The preparation method of the graphene polyurethane composite plastic for sports equipment according to claim 1, wherein the graphene polyurethane composite plastic comprises the following steps: the particle size of the mixed liquid atomized particles in the step (3) is 20-50 μm.
10. A graphene/polyurethane composite plastic for sports equipment, which is prepared by the preparation method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117924914A (en) * | 2024-03-22 | 2024-04-26 | 江苏火凤凰线缆系统技术股份有限公司 | Special cable for automobile electric side sliding door and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117924914A (en) * | 2024-03-22 | 2024-04-26 | 江苏火凤凰线缆系统技术股份有限公司 | Special cable for automobile electric side sliding door and preparation process thereof |
| CN117924914B (en) * | 2024-03-22 | 2024-06-07 | 江苏火凤凰线缆系统技术股份有限公司 | Special cable for automobile electric side sliding door and preparation process thereof |
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