CN109517231B - Elastomer composite and method for making same - Google Patents

Elastomer composite and method for making same Download PDF

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CN109517231B
CN109517231B CN201811555635.2A CN201811555635A CN109517231B CN 109517231 B CN109517231 B CN 109517231B CN 201811555635 A CN201811555635 A CN 201811555635A CN 109517231 B CN109517231 B CN 109517231B
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substrate
carbon nanotube
nanotube array
modifier
precursor
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CN109517231A (en
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邓飞
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Shenzhen Cone Technology Co ltd
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Shenzhen Cone Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention relates to an elastomer composite material and a preparation method thereof. The preparation method of the elastomer composite material comprises the following steps: respectively depositing the carbon nanotube array and a modifier on a first substrate on which the carbon nanotube array is formed and a second substrate on which the modifier is formed, wherein the modifier is a high molecular polymer with the thermal decomposition temperature of below 300 ℃; carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier to obtain a modified carbon nanotube array; and (3) uniformly mixing the modified carbon nanotube array and the precursor in a second protective gas atmosphere, reacting at 325-330 ℃ for 15-20 min, and forming to obtain the elastomer composite material, wherein the precursor is a high-molecular polymer with the thermal decomposition temperature of more than 300 ℃. The elastomer composite material can be used for preparing elastomer composite materials with better mechanical properties.

Description

Elastomer composite and method for making same
Technical Field
The invention relates to the technical field of nano materials, in particular to an elastomer composite material and a preparation method thereof.
Background
Elastomers are typically formed by mixing a base polymer with a variety of chemicals. The elastomer has a long chain and cross-linked point structure, and when stretched, the long chain structure extends within its tolerable range; when the stretching force disappears, the long chains shrink back to the original state due to the fixing effect of the cross-linking points. The elongation of the elastomer with excellent performance can reach 5-700%.
Generally, reinforcing agents, hardening agents, antioxidants, etc. are added to elastomers to enhance their mechanical properties and corrosion resistance. The conventional method adds carbon black or glass fiber and the like, which can often enhance the tensile modulus (hardness) of the composite material, but also can cause the reduction of the fracture deformation degree. In the industry of the present stage, elastomers with high tensile modulus, high fracture deformability and low density are required as raw materials, such as tires applied to the field of aviation, seal rings and blowout preventers applied to the fields of oil drilling and refining. To meet these industrial demands, carbon nanotubes have been added to enhance the tensile modulus and compression resistance of elastomer composites. However, the carbon nanotubes have the property of agglomeration, so that the carbon nanotubes are difficult to uniformly disperse, and the mechanical properties of the elastomer composite material are influenced. Some studies have modified carbon nanotubes to avoid agglomeration of the carbon nanotubes. In the traditional modification mode, substances such as strong acid or halide mainly react with the carbon nano tube, and although the agglomeration of the carbon nano tube can be improved to a certain degree, the structure of the carbon nano tube is seriously damaged, so that the mechanical property of the elastomer composite material can not meet the actual requirement.
Disclosure of Invention
Based on this, there is a need for a method for preparing an elastomer composite, which can prepare an elastomer composite having superior mechanical properties.
In addition, an elastomer composite is provided.
A method of preparing an elastomer composite comprising the steps of:
depositing a carbon nanotube array on a first substrate;
depositing a modifier on a second substrate, wherein the modifier is a high molecular polymer with the thermal decomposition temperature of below 300 ℃;
under the atmosphere of first protective gas, carrying out ultraviolet irradiation treatment on the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed, so that the modifier and the carbon nanotube array are subjected to grafting reaction to obtain a modified carbon nanotube array, wherein the irradiation power of ultraviolet light is 15-35 mW, the ultraviolet light is monochromatic narrowband light with the irradiation wavelength of 150-350 nm, and the irradiation treatment time of the ultraviolet light is 30-60 min; and
and (2) uniformly mixing the modified carbon nanotube array and the precursor in a second protective gas atmosphere, reacting at 325-330 ℃ for 15-20 min, and forming to obtain the elastomer composite material, wherein the precursor is a high-molecular polymer with the thermal decomposition temperature of more than 300 ℃.
The preparation method of the elastomer composite material comprises the steps of placing the carbon nanotube array and the modifier under ultraviolet light for ultraviolet irradiation treatment, setting the irradiation power of the ultraviolet light to be 15-35 mW, setting the ultraviolet light to be monochromatic narrow-band light with the irradiation wavelength of 150-350 nm, enabling the modifier to be grafted to the surface of the carbon nanotube array so as to increase the distance between the carbon nanotubes, thereby reducing agglomeration caused by van der Waals force between the carbon nanotubes to obtain the easily-dispersed modified carbon nanotube array, and in the process of mixing the modified carbon nanotube array, the precursor and the sulfur-based cross-linking agent to obtain the elastomer composite material, because the modifier is a high-molecular polymer with the thermal decomposition temperature of below 300 ℃ and the precursor is a high-molecular polymer with the thermal decomposition temperature of above 300 ℃, in the process of heating, the connecting bond between the carbon nanotube array and the modifier is broken so that the modified carbon nanotube array is recovered as the carbon nanotube array, the original excellent mechanical properties of the carbon nanotube array are recovered, so that the obtained elastomer composite material has excellent mechanical properties, and meanwhile, the preparation method does not need to disperse the carbon nanotube array in a solvent and then carry out subsequent treatment, so that the harm to a human body and the environment caused by using a toxic reagent is avoided. Tests prove that the elastomer composite material prepared by the preparation method has the advantages of standard tensile modulus of 85.3-87.3, elongation at break of 628-660%, and excellent mechanical properties.
In one embodiment, the modifier is selected from at least one of polymethyl methacrylate and polyoxymethylene; and/or the presence of a catalyst in the reaction mixture,
the precursor is selected from at least one of polybutadiene and polychloroprene.
In one embodiment, the mass ratio of the modified carbon nanotube array to the precursor is 0.6:100 to 0.8: 100.
In one embodiment, the step of uniformly mixing the modified carbon nanotube array and the precursor in a second protective gas atmosphere, and reacting at 325-330 ℃ for 15-20 min comprises:
mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion solution, wherein the first solvent is at least one selected from dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropanol, cyclohexane and N-methylpyrrolidone;
mixing the precursor with a second solvent to obtain a second dispersion solution, wherein the second solvent is at least one selected from dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropanol, cyclohexane and N-methylpyrrolidone; and
uniformly mixing the first dispersion liquid and the second dispersion liquid, heating to 325-330 ℃ at the speed of 10-12 ℃/min, and reacting for 15-20 min at 325-330 ℃.
In one embodiment, the mass ratio of the modified carbon nanotube array to the first solvent is 1 (100-150), and the mass ratio of the precursor to the second solvent is 1 (1-3).
In one embodiment, the step of depositing the array of carbon nanotubes on the first substrate comprises:
depositing a catalyst layer on the first substrate; and
heating the first substrate with the catalyst layer to 550-900 ℃ in a third protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array; the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of the ethylene to the hydrogen to the nitrogen is (25-40): (1-10): (70-80).
In one embodiment, the carbon nanotube array is a single-wall carbon nanotube array, the length of the carbon nanotube array is 400 μm to 600 μm, and the diameter of the carbon nanotube in the carbon nanotube array is 10nm to 15 nm; and/or the presence of a catalyst in the reaction mixture,
the thickness of the modifier deposited on the second substrate is 1 mm-5 mm; and/or the presence of a catalyst in the reaction mixture,
the first substrate is a nickel sheet or a copper sheet; and/or the presence of a catalyst in the reaction mixture,
the second substrate is a nickel sheet or a copper sheet.
In one embodiment, in the step of performing ultraviolet irradiation treatment on the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed, the first substrate and the second substrate are placed on the same horizontal plane, the first substrate has a first working surface on which the carbon nanotube array is formed, the second substrate has a second working surface on which the modifier is formed, and a gap of not more than 0.8mm is formed between the carbon nanotube array and the modifier in a horizontal direction.
In one embodiment, the first protective gas is selected from at least one of nitrogen, argon, and helium; and/or the presence of a catalyst in the reaction mixture,
the second protective gas is selected from at least one of nitrogen, argon, and helium.
An elastomer composite prepared by the method of preparing an elastomer composite described in the above example.
Drawings
FIG. 1 is a scanning electron micrograph of the elastomer composite of example 1;
FIG. 2 is an XPS plot of the carbon nanotube array of example 1;
FIG. 3 is an XPS plot of the poly (methyl methacrylate) of example 1;
FIG. 4 is an XPS plot of a modified carbon nanophotonic array of example 1;
FIG. 5 is a stress-strain comparison curve for the elastomer composites of examples 1 and 7.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A method of preparing an elastomer composite according to an embodiment includes operations S110 to S140 of:
s110, depositing a carbon nano tube array on the first substrate.
In one embodiment, the first substrate is a nickel or copper sheet. The first substrate mainly plays a role in bearing the carbon nanotube array, and the nickel sheet and the copper sheet have good stability for the carbon nanotube array and cannot react with the carbon nanotube array.
In one embodiment, the first substrate has a size of 2 inches, but in other embodiments, the first substrate may have any other size.
In one embodiment, the step of depositing the carbon nanotube array on the first substrate includes steps S111 to S112:
and S111, depositing a catalyst layer on the first substrate.
In one embodiment, a catalyst layer is formed on a surface of a first substrate using an electron beam evaporation method. Further, the material of the catalyst layer is selected from at least one of cobalt and nickel. The thickness of the catalyst layer is 20nm to 23 nm.
And S112, heating the first substrate with the catalyst layer to 550-900 ℃ in the third protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array.
In one embodiment, the third protective gas is selected from at least one of nitrogen, hydrogen, argon, and helium.
In one embodiment, the first substrate deposited with the catalyst layer is placed in a chemical vapor reaction furnace for reaction. Further, protective gas is introduced into the chemical vapor reaction furnace, and then the temperature of the chemical vapor reaction furnace is raised to 550-900 ℃ so that the catalyst layer uniformly nucleates on the first substrate; then carbon source gas is introduced into the reaction kettle for reaction.
In one embodiment, the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of the ethylene to the hydrogen to the nitrogen is (25-40): (1-10): (70-80). The flow rate of the introduced carbon source gas is 1L/min-3L/min, and the time for introducing the carbon source gas to react is 15 min-25 min.
In one embodiment, the carbon nanotubes in the carbon nanotube array deposited on the first substrate are single-walled carbon nanotubes. It should be noted that the carbon nanotubes in the carbon nanotube array deposited on the first substrate may also be multi-walled carbon nanotubes. It should be noted that, when the preparation method of the elastomer composite material is adopted, the structure of the single-wall carbon nanotube is more uniform, and the bond energy of the carbon-carbon bond is higher, so that the difficulty of surface modification of the single-wall carbon nanotube fiber with more surface wall carbon nanotube fiber is higher.
In one embodiment, the length of the carbon nanotube array deposited on the first substrate is 400 μm to 600 μm. The diameter of the carbon nano tube in the carbon nano tube array is 10 nm-15 nm.
In one embodiment, the first substrate has a first working surface, and a carbon nanotube array layer is deposited on the first working surface.
And S120, depositing a modifier on the second substrate, wherein the modifier is a high-molecular polymer with the thermal decomposition temperature of below 300 ℃.
In one embodiment, the modifier is a high molecular polymer with a thermal decomposition temperature of less than 300 ℃ and a relative molecular mass of 800-4000. The arrangement further increases the agglomeration resistance of the modified carbon nanotube array and improves the dispersibility of the modified carbon nanotube array. When the temperature is higher than 300 ℃, the entire composite material is damaged during the thermal decomposition process. When the relative molecular mass is less than 800, the anti-agglomeration effect and the dispersion effect on the carbon nano tube are not good; when the relative molecular weight is more than 4000, a case where thermal decomposition is not complete may occur. Further, the modifier is a high molecular polymer with the thermal decomposition temperature of 120-180 ℃ and the relative molecular mass of 800-4000.
In one embodiment, the modifier is selected from at least one of polymethyl methacrylate and polyoxymethylene. When the modifier contains polymethyl methacrylate, it is advantageous to improve the impact resistance and weather resistance of the elastomer composite. The modified product is not limited to the above-mentioned one, and other high molecular weight polymers having a thermal decomposition temperature of 300 ℃ or lower may be used as the modified product.
In one embodiment, the second substrate is a nickel or copper sheet. The second substrate is mainly used for bearing the modifier, and the nickel sheet and the copper sheet have good stability and cannot react with the modifier.
In one embodiment, the size of the second substrate is 50mm by 50mm, but the size of the second substrate may be any other size in other embodiments.
In one embodiment, the method of depositing the modifier on the second substrate can be by forming a thin film of the modifier on the second substrate. Of course, in other embodiments, the shear modifier material may be disposed on the second substrate.
In one embodiment, the modifier is deposited on the second substrate to a thickness of 1mm to 5 mm.
In one embodiment, the second substrate has a second working surface. And depositing the modifier on the second working surface. The modifier completely covers the second working surface.
S130, under the atmosphere of first protective gas, ultraviolet irradiation treatment is carried out on the first substrate with the carbon nanotube array and the second substrate with the modifier so as to enable the modifier and the carbon nanotube array to carry out grafting reaction, and the modified carbon nanotube array is obtained.
In one embodiment, a first substrate formed with a carbon nanotube array and a second substrate formed with a modifier are placed in the same reaction chamber. The reaction chamber can be closed, and the reaction chamber is provided with an air inlet and an air outlet. Be equipped with the ultraviolet ray subassembly in the reaction chamber, can carry out ultraviolet irradiation to the reaction chamber and handle. Further, the first substrate with the carbon nanotube array and the second substrate with the modifier are placed in the reaction chamber side by side.
In one embodiment, the first substrate with the carbon nanotube array and the second substrate with the modifier are placed side by side, so that the carbon nanotubes on the first substrate and the modifier on the second substrate are on the same horizontal plane. Further, the carbon nanotube array and the modifier form a gap of not more than 0.8mm in the horizontal direction. Preferably, the carbon nanotube array and the modifier are in direct contact.
In one embodiment, in the process of performing ultraviolet irradiation treatment on the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed, first, the gas inlet and the gas outlet of the reaction chamber are closed, and the reaction chamber is vacuumized to reduce the pressure in the reaction chamber to 10 deg.f-2The Torr is less. Preferably, the gas pressure in the reaction chamber is reduced to 10- 6The Torr is less. And secondly, introducing a first protective gas into the reaction cavity through the gas inlet until the pressure reaches normal atmospheric pressure, opening the gas outlet, and continuously introducing the first protective gas to maintain the pressure of the system.
In one embodiment, the flow rate of the first protective gas is between 2L/min and 3L/min. The first protective gas is selected from at least one of nitrogen, argon, and helium.
In one embodiment, the irradiation power of the ultraviolet light is 15mW to 35mW when the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed are subjected to the ultraviolet light irradiation treatment. Under the irradiation power, the heat effect of the reaction system is improved, the temperature of the system is increased to a state that the high molecular polymer forms a gas state, and the gas moves to the surface of the carbon nano tube array to perform graft polymerization with the carbon nano tube array under the action of the first protective gas flow.
In one embodiment, the irradiation power of the ultraviolet light is 15mW to 25mW when the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed are subjected to the ultraviolet light irradiation treatment. In one embodiment, the irradiation power of the ultraviolet light is 25mW to 35mW when the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed are subjected to the ultraviolet light irradiation treatment. In one embodiment, the irradiation power of the ultraviolet light is 22mW to 33mW when the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed are subjected to the ultraviolet light irradiation treatment.
In one embodiment, the ultraviolet light is monochromatic (monochromatic) narrow band light with an illumination wavelength of 150nm to 350 nm. Further, the monochromatic narrow-band light is monochromatic light with the bandwidth of 200 nm-350 nm. In one embodiment, the ultraviolet light is monochromatic narrow-band light with an irradiation wavelength of 200nm to 298 nm. In one embodiment, the ultraviolet light is monochromatic narrow-band light with an irradiation wavelength of 298nm to 350 nm. In one embodiment, the ultraviolet light is monochromatic narrow-band light with an irradiation wavelength of 260nm to 330 nm.
Further, the irradiation wavelength of the ultraviolet light is calculated by the following formula:
λ1＝Nhc/δ1，λ2＝Nhc/δ2；
λ≤min{λ1，λ2}；
wherein, λ is the irradiation wavelength of ultraviolet light, N is the Avogastron constant, h is the Planck constant, and c is the wavelength; δ 1 is the bond energy of the C ═ C bond in the carbon nanotube array, and λ 1 is the ultraviolet irradiation wavelength at which the C ═ C bond in the carbon nanotube array is broken; δ 2 is the bond energy of the C — C bond or C ═ C bond in the modified product, and λ 2 is the ultraviolet irradiation wavelength at which the C — C bond or C ═ C bond in the modified product is cleaved.
Further, δ 2 is a bond energy of a C — C bond or C ═ C bond in the main chain of the modified product. When the ultraviolet irradiation treatment is performed, the main chain of the modified substance is broken and grafted onto the carbon nanotube array again.
It is understood that the shorter the irradiation wavelength of the ultraviolet light, the greater the photon energy generated by the ultraviolet light, and λ 1 is the maximum wavelength for opening C ═ C bonds in the carbon nanotube array, and λ 2 is the maximum wavelength for opening C — C bonds or C ═ C bonds in the modifier, and when the irradiation wavelength of the ultraviolet light is ≦ min { λ 1, λ 2}, the modifier can be grafted to the carbon nanotube array.
Further, the irradiation wavelength of the ultraviolet light is min { λ 1, λ 2 }. Under the condition, the damage of ultraviolet light to the modifier and the carbon nano tube array structure is reduced under the condition of ensuring that the modifier can be grafted to the carbon nano tube array.
In one embodiment, the distance between the ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed is 2 mm-20 mm. In one embodiment, the distance between the ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed is 5-18 mm. In one embodiment, the distance between the ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed is 10-15 mm.
In one embodiment, the ultraviolet irradiation treatment is performed for 20min to 50 min. In one embodiment, the ultraviolet irradiation treatment is performed for 20min to 35 min. In one embodiment, the ultraviolet irradiation treatment is performed for 35min to 50 min. In one embodiment, the ultraviolet irradiation treatment is performed for 33min to 45 min.
In one embodiment, the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed are subjected to ultraviolet irradiation treatment, wherein the irradiation power of ultraviolet light is 22 mW-33 mW, the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 260 nm-330 nm, and the ultraviolet irradiation treatment time is 33 min-45 min. Under the condition, the damage of ultraviolet light to the modifier and the carbon nano tube array structure is reduced under the condition of ensuring that the modifier can be grafted to the carbon nano tube array, so that the mechanical property of the elastomer composite material is further improved.
In one embodiment, after the ultraviolet irradiation treatment is performed on the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed, the operation of placing the first substrate in a protective gas atmosphere and naturally cooling the first substrate is further included. In other embodiments, the operation of placing the first substrate in a protective gas atmosphere for natural cooling may be omitted.
In one embodiment, the first substrate is placed in a first protective gas atmosphere for natural cooling operation, and the protective gas is at least one selected from nitrogen, argon, and helium. Placing the first substrate in a protective gas atmosphere for natural cooling can prevent the carbon nanotube array from being oxidized by exposure to air.
And S140, uniformly mixing the modified carbon nanotube array and the precursor in a second protective gas atmosphere, reacting at 325-330 ℃ for 15-20 min, and forming to obtain the elastomer composite material. The precursor is a high molecular polymer with the thermal decomposition temperature of more than 300 ℃.
In the process of mixing the modified carbon nanotube array, the precursor and the sulfur-based cross-linking agent to obtain the elastomer composite material, because the modifier is a high-molecular polymer with the thermal decomposition temperature of below 300 ℃ and the precursor is a high-molecular polymer with the thermal decomposition temperature of above 300 ℃, in the process of heating, the connecting bond between the carbon nanotube array and the modifier is broken to recover the modified carbon nanotube array into the carbon nanotube array so as to recover the original excellent mechanical property of the carbon nanotube array, and therefore the obtained elastomer composite material has excellent mechanical property.
In one embodiment, the precursor is a high molecular polymer with a thermal decomposition temperature of 300 ℃ or higher and a relative molecular mass of 800-4000. The arrangement further increases the mechanical property of the elastomer composite material. Further, the precursor is a high molecular polymer with the thermal decomposition temperature of 340-380 ℃ and the relative molecular mass of 800-4000.
In one embodiment, the precursor is selected from at least one of polybutadiene and polychloroprene. The precursor is not limited to the above-mentioned ones, and other high molecular weight polymers having a thermal decomposition temperature of 300 ℃ or higher may be used as the precursor. In one embodiment, the mass ratio of the modified carbon nanotube array to the precursor is 0.6:100 to 0.8: 100. In one embodiment, the mass ratio of the modified carbon nanotube array to the precursor is 0.4: 100-0.7: 100: 1.35. In one embodiment, the mass ratio of the modified carbon nanotube array to the precursor is 0.7:100 to 0.8: 100.
In one embodiment, the second protective gas is selected from at least one of nitrogen, argon, and helium.
In one embodiment, the step of uniformly mixing the modified carbon nanotube array and the precursor in a second protective gas atmosphere, and reacting at 325-330 ℃ for 15-20 min comprises: mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid; mixing the precursor with a second solvent to obtain a second dispersion liquid; and uniformly mixing the first dispersion liquid and the second dispersion liquid, heating to 325-330 ℃ at the speed of 10-12 ℃/min, and reacting for 15-20 min at 325-330 ℃.
Further, the first solvent is at least one selected from the group consisting of dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropyl alcohol, cyclohexane and N-methylpyrrolidone.
The second solvent is at least one selected from dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropanol, cyclohexane and N-methylpyrrolidone.
The mass ratio of the modified carbon nanotube array to the first solvent is 1 (100-150). The mass ratio of the precursor to the second solvent is 1 (1-3).
The step of uniformly mixing the first dispersion liquid and the second dispersion liquid comprises the following specific steps: and mixing the first dispersion liquid and the second dispersion liquid, carrying out ultrasonic treatment for 1-2 h, and stirring at 150-400 rpm for 20-30 min to form a mixed solution of the modified carbon nanotube array and the precursor. Further, the stirring manner is grinding.
In the molding operation, a conventional mold molding method is used. It should be noted that the modified carbon nanotube array, the precursor and the cross-linking substance may be uniformly mixed and then added into a mold for molding, or the modified carbon nanotube array and the precursor may be uniformly mixed and then added into the mold, and then the cross-linking substance is added for continuous mixing and then molding.
The preparation method of the elastomer composite material comprises the steps of placing the carbon nanotube array and the modifier under ultraviolet light for ultraviolet irradiation treatment, setting the irradiation power of the ultraviolet light to be 15-35 mW, setting the ultraviolet light to be monochromatic narrow-band light with the irradiation wavelength of 150-350 nm, enabling the modifier to be grafted to the surface of the carbon nanotube array so as to increase the distance between the carbon nanotubes, thereby reducing agglomeration caused by van der Waals force between the carbon nanotubes to obtain the easily-dispersed modified carbon nanotube array, and in the process of mixing the modified carbon nanotube array, the precursor and the sulfur-based cross-linking agent to obtain the elastomer composite material, because the modifier is a high-molecular polymer with the thermal decomposition temperature of below 300 ℃ and the precursor is a high-molecular polymer with the thermal decomposition temperature of above 300 ℃, in the process of heating, the connecting bond between the carbon nanotube array and the modifier is broken so that the modified carbon nanotube array is recovered as the carbon nanotube array, and then the original excellent mechanical properties are recovered, so that the obtained elastomer composite material has excellent mechanical properties, and meanwhile, the preparation method does not need to disperse the carbon nanotube array in a solvent and then carry out subsequent treatment, thereby avoiding the harm to human bodies and the environment caused by using toxic reagents. Tests prove that the elastomer composite material prepared by the preparation method has the advantages of standard tensile modulus of 85.3-87.3, elongation at break of 628-660%, and excellent mechanical properties.
In addition, in the preparation method of the elastomer composite material, the prepared elastic composite material has excellent mechanical property and can be applied to sealing materials with high temperature and high pressure resistance and high corrosion resistance, and meanwhile, the preparation method of the elastomer composite material can also be used for preparing a modified carbon nanotube array which is easy to disperse, so that the modified carbon nanotube array can be used for preparing composite materials with stronger mechanical property and higher requirement on dispersion property.
Thirdly, the preparation method of the elastomer composite material takes the high molecular polymer as the raw material to prepare the modified carbon nanotube array, is convenient for operation and reaction control, can directly modify the high molecular polymer on the surface of the carbon nanotube array, does not need multiple modification and treatment, reduces the reaction procedures, and is beneficial to improving the reaction efficiency and reducing the synthesis cost.
In addition, in the preparation method of the elastomer composite material, the carbon nanotube array does not need to be dispersed in the solvent and then subjected to subsequent treatment, namely, the operation of removing the solvent is not needed, the process is simplified, meanwhile, no solvent and the like remain, the purity of the modified carbon nanotube array is higher, and the mechanical property of the elastomer composite material is further ensured.
The following are portions of specific embodiments.
Unless otherwise specified, the following examples contain no other components not specifically indicated except for inevitable impurities.
In the following examples, unless otherwise specified, XPS spectroscopy was performed using an EA 125 spectrometer, a non-chromatographic aluminum X-ray source (1486.5 eV); the scanning electron microscope test was performed using JEM-7400F from JEOL. The ultraviolet light is monochromatic light with the bandwidth of 300 nm. The first substrate is a copper sheet. The second substrate is a nickel sheet.
Example 1
Taking a first substrate, depositing a catalyst layer with the thickness of 20nm on the first substrate, wherein the catalyst layer is cobalt, placing the first substrate in a chemical vapor deposition reaction furnace, introducing argon, heating to 550 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of the ethylene, the hydrogen and the nitrogen is 25:1:7) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 1L/min, reacting for 15min, so that the surface of the first substrate is completely covered with a carbon nanotube array, the carbon nanotube array is a single-walled carbon nanotube array, the length of the carbon nanotube array is 400 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 10 nm; taking a second substrate, and forming a modifier with the thickness of 5mm on the second substrate, wherein the modifier is polymethyl methacrylate, and the relative molecular mass of the modifier is 800.
Placing the first substrate with the carbon nanotube array and the second substrate with the modifier in a reaction chamber side by side, wherein the first substrate with the carbon nanotube array and the second substrate with the modifier are in the same horizontal plane, the carbon nanotube array and the modifier are in contact, and vacuumizing the reaction chamber until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the distance between an ultraviolet light source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 2mm, the irradiation power of ultraviolet light is 15mW, the irradiation wavelength of the ultraviolet light is 150nm, and the irradiation time is 30 min; closing the ultraviolet light assembly, exposing the first substrate to nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbonAn array of nanotubes.
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is methyl ethyl ketone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 100; mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is methyl ethyl ketone, the mass ratio of the precursor to the second solvent is 1:2, the precursor is polybutadiene, and the relative molecular mass of the precursor is 4000; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1 hour, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.6: 100. And heating the mixed solution to 325 ℃ at the speed of 10 ℃/min, reacting at 325 ℃ for 15min, and forming to obtain the elastomer composite material.
Example 2
Taking a first substrate, depositing a catalyst layer with the thickness of 23nm on the first substrate, wherein the catalyst layer is iron, placing the first substrate in a chemical vapor deposition reaction furnace, introducing helium, heating to 900 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of the ethylene, the hydrogen and the nitrogen is 4:1:8) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 3L/min, reacting for 25min, so that the surface of the first substrate is completely covered with a carbon nanotube array, the carbon nanotube array is a single-walled carbon nanotube array, the length of the carbon nanotube array is 600 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 15 nm; taking a second substrate, and forming a modifier with the thickness of 1mm on the second substrate, wherein the modifier is polyformaldehyde, and the relative molecular mass of the modifier is 4000.
Placing the first substrate with the carbon nanotube array and the second substrate with the modifier in a reaction chamber side by side, wherein the first substrate with the carbon nanotube array and the second substrate with the modifier are in the same horizontal plane, the carbon nanotube array and the modifier are in contact, and vacuumizing the reaction chamber until the air pressure is reduced to 10-2Introducing nitrogen after the Torr, keeping the flow rate of the nitrogen at 3L/min, and performing ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the ultraviolet isThe distance between the source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 20mm, the irradiation power of ultraviolet light is 35mW, the irradiation wavelength of the ultraviolet light is 350nm, and the irradiation time is 60 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is isopropanol, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 150; mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is isopropanol, the mass ratio of the precursor to the second solvent is 1:3, the precursor is polychloroprene, and the relative molecular mass of the precursor is 800; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 2 hours, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.8: 100. And heating the mixed solution to 330 ℃ at the speed of 12 ℃/min, reacting at 330 ℃ for 20min, and forming to obtain the elastomer composite material.
Example 3
Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, introducing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of ethylene, hydrogen and nitrogen is 6:1:15) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 2L/min, and reacting for 20min, so that the surface of the first substrate is completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, the length of the carbon nanotube array is 500 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm; taking a second substrate, and forming a modifier with the thickness of 3mm on the second substrate, wherein the modifier comprises a mixture of a first component and a second component in a molar ratio of 3.2: 1, the relative molecular mass of the polymethyl methacrylate is 1500, and the relative molecular mass of the polyformaldehyde is 1000.
First formed with carbon nanotube arrayThe substrate and the second substrate with the modifier are arranged in the reaction cavity side by side, the first substrate with the carbon nanotube array and the second substrate with the modifier are positioned on the same horizontal plane, the carbon nanotube array is contacted with the modifier, the reaction cavity is vacuumized until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the distance between an ultraviolet source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 10mm, the irradiation power of ultraviolet is 25mW, the irradiation wavelength of the ultraviolet is 298nm, and the irradiation time is 45 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is acetone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 120; and mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is acetone, the mass ratio of the precursor to the second solvent is 1:2, and the molar ratio of the precursor is 0.5: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1.5h, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.7: 100. And heating the mixed solution to 327 ℃ at the speed of 11 ℃/min, reacting at 327 ℃ for 18min, and molding to obtain the elastomer composite material.
Example 4
Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, introducing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of ethylene, hydrogen and nitrogen is 6:1:15) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 2L/min, and reacting for 20min, so that the surface of the first substrate is completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, the length of the carbon nanotube array is 500 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm; a second substrate was taken, and a modifier having a thickness of 3mm was formed on the second substrate, the modifier being polyethylene having a relative molecular mass of 2500.
Placing the first substrate with the carbon nanotube array and the second substrate with the modifier in a reaction chamber side by side, wherein the first substrate with the carbon nanotube array and the second substrate with the modifier are in the same horizontal plane, the carbon nanotube array and the modifier are in contact, and vacuumizing the reaction chamber until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the distance between an ultraviolet source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 10mm, the irradiation power of ultraviolet is 25mW, the irradiation wavelength of the ultraviolet is 298nm, and the irradiation time is 45 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is acetone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 120; and mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is acetone, the mass ratio of the precursor to the second solvent is 1:2, and the molar ratio of the precursor is 0.5: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1.5h, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.7: 100. And heating the mixed solution to 327 ℃ at the speed of 11 ℃/min, reacting at 327 ℃ for 18min, and molding to obtain the elastomer composite material.
Example 5
Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, introducing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of ethylene, hydrogen and nitrogen is 6:1:15) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 2L/min, and reacting for 20min, so that the surface of the first substrate is completely covered with a carbon nanotube array which is a multi-walled carbon nanotube array, the length of the carbon nanotube array is 500 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm; taking a second substrate, and forming a modifier with the thickness of 3mm on the second substrate, wherein the modifier comprises a mixture of a first component and a second component in a molar ratio of 3.2: 1, the relative molecular mass of the polymethyl methacrylate is 1500, and the relative molecular mass of the polyformaldehyde is 1000.
Placing the first substrate with the carbon nanotube array and the second substrate with the modifier in a reaction chamber side by side, wherein the first substrate with the carbon nanotube array and the second substrate with the modifier are in the same horizontal plane, the carbon nanotube array and the modifier are in contact, and vacuumizing the reaction chamber until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the distance between an ultraviolet source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 10mm, the irradiation power of ultraviolet is 25mW, the irradiation wavelength of the ultraviolet is 298nm, and the irradiation time is 45 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is acetone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 120; and mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is acetone, the mass ratio of the precursor to the second solvent is 1:2, and the mass ratio of the precursor to the second solvent is 0.5: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1.5h, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.7: 100. And heating the mixed solution to 327 ℃ at the speed of 11 ℃/min, reacting at 327 ℃ for 18min, and molding to obtain the elastomer composite material.
Example 6
Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, introducing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of ethylene, hydrogen and nitrogen is 6:1:15) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 2L/min, and reacting for 20min, so that the surface of the first substrate is completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, the length of the carbon nanotube array is 500 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm.
Mixing the carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is acetone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 120; and mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is acetone, the mass ratio of the precursor to the second solvent is 1:2, and the mass ratio of the precursor to the second solvent is 0.5: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1.5h, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the carbon nanotube array to the precursor is 0.7: 100. And heating the mixed solution to 327 ℃ at the speed of 11 ℃/min, reacting at 327 ℃ for 18min, and molding to obtain the elastomer composite material.
Example 7
Mixing tetraethoxysilane and a precursor in a mass ratio of 0.1: 1, uniformly mixing, heating to 327 ℃ at the speed of 11 ℃/min, reacting at 327 ℃ for 18min, and molding to obtain the elastomer composite material, wherein the precursor is prepared from the following components in percentage by mass: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500.
Example 8
Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, introducing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of ethylene, hydrogen and nitrogen is 6:1:15) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 2L/min, and reacting for 20min, so that the surface of the first substrate is completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, the length of the carbon nanotube array is 500 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm; taking a second substrate, and forming a modifier with the thickness of 3mm on the second substrate, wherein the modifier comprises a mixture of a first component and a second component in a molar ratio of 3.2: 1, the relative molecular mass of the polymethyl methacrylate is 1500, and the relative molecular mass of the polyformaldehyde is 1000.
Placing the first substrate with the carbon nanotube array and the second substrate with the modifier in a reaction chamber side by side, wherein the first substrate with the carbon nanotube array and the second substrate with the modifier are in the same horizontal plane, the carbon nanotube array and the modifier are in contact, and vacuumizing the reaction chamber until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the modifier, wherein the distance between an ultraviolet source and the first substrate with the carbon nanotube array and the second substrate with the modifier is 10mm, the irradiation power of ultraviolet is 25mW, the irradiation wavelength of the ultraviolet is 298nm, and the irradiation time is 45 min; closing the ultraviolet light assembly, exposing the first substrate in a nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array。
Mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion liquid, wherein the first solvent is acetone, and the mass ratio of the modified carbon nanotube array to the first solvent is 1: 120; and mixing the precursor with a second solvent to obtain a second dispersion liquid, wherein the second solvent is acetone, the mass ratio of the precursor to the second solvent is 1:2, and the molar ratio of the precursor is 0.5: 1, the relative molecular mass of polybutadiene is 1500, and the relative molecular mass of polychloroprene is 1500; and mixing the first dispersion liquid and the second dispersion liquid, performing ultrasonic treatment for 1.5h, and fully grinding in a mortar to obtain a mixed liquid, wherein the mass ratio of the modified carbon nanotube array to the precursor is 0.7: 100. And heating the mixed solution to 280 ℃ at the speed of 11 ℃/min, reacting at 280 ℃ for 18min, and forming to obtain the elastomer composite material.
And (3) testing:
(1) the elastomer composite of example 1 was subjected to scanning electron microscope testing, and the results are shown in fig. 1. Wherein FIG. 1 is a scanning electron micrograph of the elastomer composite of example 1 at a concentration of 5phr (per hundred rubber).
As can be seen from fig. 1, the carbon nanotube array of the elastomer composite of example 1 was uniformly dispersed.
(2) XPS spectroscopy was performed on the carbon nanotube array (i.e., the unmodified carbon nanotube array), the polymethyl methacrylate, and the modified carbon nanotube array in example 1, and the results are shown in fig. 2 to 4. Fig. 2 is an XPS diagram of a carbon nanotube array, fig. 3 is an XPS diagram of polymethyl methacrylate, and fig. 4 is an XPS diagram of a modified carbon nano light array.
As can be seen from fig. 2 to 4, two peaks appear in the sample after the modification of the carbon nanotube array, and correspond to the peak positions of the carbon nanotube array and the polymethyl methacrylate, respectively, which further illustrates that the high molecular polymer is grafted to the carbon nanotube array after the high-energy ultraviolet light treatment.
(3) The stress-strain curves of the elastomer composites of examples 1 and 7 were determined by the tensile test method and the results are shown in FIG. 5. FIG. 5 is a stress-strain comparison curve for the elastomer composites of examples 1 and 7.
As can be seen from fig. 5, the young's modulus and tensile strength of the elastomer composite material added with the modified carbon nanotubes are greatly increased.
(4) The mechanical properties of the elastomer composites of examples 1-8 were measured and the results are detailed in table 1.
Specifically, tensile strength (MPA) of each of the above materials was measured by ASTM D-412 method, and normalized tensile modulus was calculated by the formula:
Figure BDA0001911810700000231
wherein Y is the Young's modulus of the elastomer composites of examples 1-8, and Y iscontrolIs the young's modulus of the elastomer composite of example 7; y and YcontrolThe ratio of (d) represents: a change in Young's modulus of the elastomer composite of examples 1 to 8 with the elastomer composite of example 7;
each of the above materials was tested for elongation at break (%) by the method of ASTM D-412.
Table 1 shows the mechanical properties of the elastomer composites of examples 1 to 8.
TABLE 1
Figure BDA0001911810700000232
Figure BDA0001911810700000241
As can be seen from Table 1, the elastomer composites of examples 1-3 and 5 have normalized tensile modulus of 85.3-87.3 and elongation at break of 628-660%, which are superior to those of example 6, and thus the elastomer composites obtained by adding the modified carbon nanotube array have higher tensile modulus and higher elongation at break. The normalized tensile modulus of the elastomer composites of examples 1 to 3 and 5 is about 80 times that of example 7, while the elongation at break of the elastomer composites of examples 1 to 3 and 5 is slightly lower than that of example 7, which shows that the elastomer composites obtained in the above embodiment have both higher tensile modulus and higher elongation at break, and have better mechanical properties.
Further, the tensile modulus and the elongation at break of the elastomer composite of example 3 are superior to those of example 4, and it is demonstrated that the mechanical properties of the elastomer composite can be improved by selecting a high molecular polymer having a thermal decomposition temperature of 300 ℃ or lower as a modifier. The tensile modulus and the elongation at break of the elastomer composite material in example 3, which are controlled by the decomposition temperature, are superior to those of example 8, which shows that the bond between the carbon nanotube array and the modified material is broken by controlling the decomposition temperature, and the modified carbon nanotube array can be restored to the carbon nanotube array to restore the original mechanical properties thereof, so that the obtained elastomer composite material has excellent mechanical properties.
(5) The swelling degree of the elastomer composites of examples 1 to 8 was measured by a volumetric method, and the measurement results are shown in Table 2. Specifically, the elastomer composites of examples 1 to 8 were taken at the same volume, the elastomer composites of examples 1 to 8 were immersed in water for 2 hours, the volume change of the elastomer composites before and after immersion was measured, and the degree of swelling, which is the ratio of the volume difference before and after immersion to the volume before immersion, was calculated.
TABLE 2 swelling degree of elastomer composites of examples 1-8
Degree of swelling (%)
Example 1 55
Example 2 50
Example 3 53
Example 4 55
Example 5 52
Example 6 70
Example 7 57
Example 8 50
As can be seen from table 2, the elastomer composite materials of examples 1 to 3 and 5 have an expansion degree of 50% to 55%, and the elastomer composite materials of examples 1 to 3 and 5 have a good crosslinking degree, and further, the modified carbon nanotube array in the above embodiment can be well crosslinked with the precursor. The swelling degree of the elastomer composite materials of examples 1 to 3 and 5 is lower than that of example 7, which shows that the crosslinking effect of the modified carbon nanotube arrays of examples 1 to 3 and 5 is better than that of tetraethoxysilane of example 7, and further shows that the modified carbon nanotube arrays obtained by the above embodiments can be used as a crosslinking agent to replace a conventional crosslinking agent to prepare the elastomer composite material.
In summary, the modified carbon nanotube array of the above embodiment can be used as a cross-linking agent to react with a precursor to prepare an elastomer composite material with excellent mechanical properties.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method of preparing an elastomer composite, comprising the steps of:
depositing a carbon nanotube array on a first substrate;
depositing a modifier on a second substrate, wherein the modifier is a high molecular polymer with the thermal decomposition temperature of below 300 ℃ and the relative molecular mass of 800-4000;
under the atmosphere of first protective gas, carrying out ultraviolet irradiation treatment on the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed, so that the modifier and the carbon nanotube array are subjected to grafting reaction to obtain a modified carbon nanotube array, wherein the irradiation power of ultraviolet light is 15-35 mW, the ultraviolet light is monochromatic narrowband light with the irradiation wavelength of 150-350 nm, and the irradiation treatment time of the ultraviolet light is 30-60 min; and
uniformly mixing the modified carbon nanotube array and a precursor in a second protective gas atmosphere, reacting at 325-330 ℃ for 15-20 min, and forming to obtain an elastomer composite material, wherein the precursor is a high-molecular polymer with the thermal decomposition temperature of more than 300 ℃;
the modifier is at least one selected from polymethyl methacrylate and polyformaldehyde;
the precursor is selected from at least one of polybutadiene and polychloroprene;
the mass ratio of the modified carbon nanotube array to the precursor is 0.6: 100-0.8: 100.
2. The method of claim 1, wherein the flow rate of the first shielding gas is 2L/min to 3L/min.
3. The method of claim 1, wherein a distance between the ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed is 2mm to 20 mm.
4. The method for preparing the elastomer composite material according to claim 1, wherein the step of uniformly mixing the modified carbon nanotube array and the precursor in the second protective gas atmosphere and reacting at 325-330 ℃ for 15-20 min comprises:
mixing the modified carbon nanotube array with a first solvent to obtain a first dispersion solution, wherein the first solvent is at least one selected from dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropanol, cyclohexane and N-methylpyrrolidone;
mixing the precursor with a second solvent to obtain a second dispersion solution, wherein the second solvent is at least one selected from dichlorobenzene, tetrahydrofuran, N-dimethylformamide, chloroform, acetone, methyl ethyl ketone, isopropanol, cyclohexane and N-methylpyrrolidone; and
uniformly mixing the first dispersion liquid and the second dispersion liquid, heating to 325-330 ℃ at the speed of 10-12 ℃/min, and reacting for 15-20 min at 325-330 ℃.
5. The method for preparing the elastomer composite material according to claim 4, wherein the mass ratio of the modified carbon nanotube array to the first solvent is 1 (100-150), and the mass ratio of the precursor to the second solvent is 1 (1-3).
6. The method of claim 1, wherein the step of depositing the array of carbon nanotubes on the first substrate comprises:
depositing a catalyst layer on the first substrate; and
heating the first substrate with the catalyst layer to 550-900 ℃ in a third protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array; the carbon source gas comprises ethylene, hydrogen and nitrogen, and the gas partial pressure ratio of the ethylene to the hydrogen to the nitrogen is (25-40): (1-10): (70-80).
7. The method of claim 1, wherein the array of carbon nanotubes is an array of single-walled carbon nanotubes, the length of the array of carbon nanotubes is 400 to 600 μ ι η, and the diameter of the carbon nanotubes in the array of carbon nanotubes is 10 to 15 nm; and/or the presence of a catalyst in the reaction mixture,
the thickness of the modifier deposited on the second substrate is 1 mm-5 mm; and/or the presence of a catalyst in the reaction mixture,
the first substrate is a nickel sheet or a copper sheet; and/or the presence of a catalyst in the reaction mixture,
the second substrate is a nickel sheet or a copper sheet.
8. The method according to claim 1, wherein in the step of irradiating the first substrate on which the carbon nanotube array is formed and the second substrate on which the modifier is formed with ultraviolet light, the first substrate and the second substrate are placed on the same horizontal plane, the first substrate has a first working surface on which the carbon nanotube array is formed, the second substrate has a second working surface on which the modifier is formed, and a gap of not more than 0.8mm is formed between the carbon nanotube array and the modifier in a horizontal direction.
9. The method of preparing an elastomer composite of claim 1, wherein the first protective gas is selected from at least one of nitrogen, argon, and helium; and/or the presence of a catalyst in the reaction mixture,
the second protective gas is selected from at least one of nitrogen, argon, and helium.
10. An elastomer composite material, characterized by being produced by the method for producing an elastomer composite material according to any one of claims 1 to 9.
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