CN109306094B - Preparation method of graphene rubber master batch - Google Patents
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- CN109306094B CN109306094B CN201811213076.7A CN201811213076A CN109306094B CN 109306094 B CN109306094 B CN 109306094B CN 201811213076 A CN201811213076 A CN 201811213076A CN 109306094 B CN109306094 B CN 109306094B
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- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
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Abstract
The invention provides a preparation method of a graphene rubber master batch, which comprises the following steps: (1) modifying the surface of graphene; (2) mixing the mixed components containing the modified graphene in the step (1) and the chloroprene rubber to form modified graphene-chloroprene rubber; (3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber; (4) and (3) mixing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) according to the weight ratio of 15-2:1, and curing and crushing to form particles to obtain the graphene rubber master batch. The graphene rubber master batch prepared by the invention can obviously improve the tensile strength and the elongation at break of the rubber material. In addition, the invention provides a novel idea for improving the mechanical property of the rubber product by using the graphene.
Description
Technical Field
The invention relates to the technical field of modification of polymer rubber materials, in particular to the technical field of modification of graphene rubber.
Background
The chloroprene rubber is mainly in a trans-1, 4 structure, and has regular molecular arrangement and reversible crystallization property; the conjugated effect and the inducing effect generated by the double bond carbon atoms on the molecular chain and the chloride ions connected with the double bond carbon atoms reduce the reaction activity of the double bond and the chloride atoms, and the structure is more stable. The chloroprene rubber is used as a general high polymer material, has the advantages of light resistance, heat resistance, cold resistance, chemical corrosion resistance and the like, is often used as a raw material of cables, conveyor belts, adhesive tapes, adhesives and the like, and is widely applied to industries and fields of national defense, buildings, traffic, light industry and the like.
Graphene is a unique single-atomic-layer two-dimensional structure material, has high carrier mobility, thermal conductivity, specific surface area, light transmittance and excellent mechanical properties, and becomes an ideal carbon material for preparing polymer composite materials. The Young modulus of the graphene can reach 1100GPa, the breaking strength reaches 125GPa, and the mechanical property of the rubber can be obviously improved by mixing the graphene with the rubber material. In addition, from the viewpoint of the effect of modifying rubber, graphene has a stronger performance improvement effect than other carbon-based materials such as carbon nanotubes and carbon black.
However, the technical effect obtained by using graphene for rubber modification is limited at present, and is mainly limited by the dispersion degree of graphene in rubber and the interaction between graphene and an interface. In order to solve the above technical problems, chinese patent publication CN105419129A discloses a preparation method of a graphene-halogenated butyl rubber composite material: adding a surfactant into the graphene oxide dispersion liquid to react to obtain a functionalized graphene oxide dispersion liquid; adding a reducing agent into the functionalized graphene oxide dispersion liquid for reaction, and then cleaning and filtering to obtain a functionalized graphene precipitate; dispersing the functionalized graphene precipitate in an organic solvent to obtain a functionalized graphene dispersion liquid; uniformly mixing the functionalized graphene dispersion liquid with halogenated butyl rubber latex to obtain a graphene-halogenated butyl rubber suspension; and curing the graphene-halogenated butyl rubber suspension to obtain the graphene-halogenated butyl rubber composite material. Chinese patent publication CN108003626A discloses a method for preparing conductive silicone rubber: mixing carbon nanotubes and graphene with silicone rubber and a vulcanizing agent to obtain a rubber compound, wherein at least one of the carbon nanotubes and the graphene is subjected to modification treatment; and vulcanizing the rubber compound to obtain the conductive rubber. The above method has either a problem of complicated process or a problem of limited effect of improving the rubber properties.
Therefore, at present, a preparation method of the graphene rubber master batch which is simple to operate and has a good rubber performance improvement effect needs to be developed.
Disclosure of Invention
The invention provides a preparation method of a graphene rubber master batch, which changes the conventional idea of improving the dispersibility of graphene and provides a graphene rubber modification method with simple operation, low cost and obvious effect by a brand new idea.
The invention provides a preparation method of a graphene rubber master batch, which comprises the following steps:
(1) modifying the surface of graphene;
(2) mixing the mixed components containing the modified graphene in the step (1) and the chloroprene rubber to form modified graphene-chloroprene rubber;
(3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber;
(4) and (3) mixing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) according to the weight ratio of 15-2:1, and curing and crushing to form particles to obtain the graphene rubber master batch.
And (2) carrying out carbonylation modification treatment on the graphene in the step (1).
And (2) pouring 100g of graphene into 100mL of absolute ethyl alcohol in the step (1) for ultrasonic treatment for 30min to form a uniform graphene-ethanol dispersion liquid, dropwise adding hydrochloric acid to adjust the pH value to 3.2-3.8, continuously dropwise adding 0.1g of silane coupling agent, stirring and reacting in a constant-temperature water bath at 50 ℃ for 5h, centrifugally separating out solids, cleaning and drying.
And (2) washing the solid obtained by centrifugation to be neutral by using deionized water in the step (1).
The weight ratio of the chloroprene rubber to the modified graphene in the step (2) is 25-10: 1; preferably, the weight ratio of the chloroprene rubber to the modified graphene in the step (2) is 20-10: 1.
The mixing temperature in the step (2) is 35-45 ℃.
The mixing temperature in the step (3) is 30-40 ℃.
The weight ratio of the nitrile rubber to the graphene in the step (3) is 50-30: 1; preferably, the weight ratio of the nitrile rubber to the graphene in the step (3) is 45-35: 1.
Preferably, the weight ratio of the modified graphene-chloroprene rubber to the graphene-nitrile rubber in the step (4) is 12-3: 1.
More preferably, the weight ratio of the modified graphene-chloroprene rubber and the graphene-nitrile rubber in the step (4) is 10-5: 1.
And (4) respectively passing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) through a thin tube for 5 times, and then putting the obtained product into an internal mixer to be mixed uniformly, wherein the mixing temperature is 35-55 ℃, the rotating speed of the internal mixer is 60-100r/min, and the mixing time is 10-40 min.
Preferably, the mixing temperature of the modified graphene-chloroprene rubber and the graphene-nitrile rubber in the step (4) is 50 ℃.
The graphene rubber master batch prepared by the preparation method.
The application of the graphene rubber master batch in preparing rubber materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a novel method for improving the rubber modification effect of graphene, which comprises the steps of preparing modified graphene-chloroprene rubber and graphene-nitrile rubber respectively, and mixing the modified graphene-chloroprene rubber and the graphene-nitrile rubber according to a certain proportion to obtain a graphene rubber master batch with a good modification effect.
(2) The invention unexpectedly discovers that when the content of the graphene in the modified graphene-chloroprene rubber is higher than that of the graphene in the graphene-nitrile rubber, a better modification effect can be obtained.
(3) According to the invention, the rubber materials containing different concentrations of graphene are mixed, so that a higher performance improvement effect is obtained, the requirement on the dispersion degree of the graphene in the rubber is reduced, and the operation steps are simplified.
Detailed Description
Example 1 preparation method of graphene rubber masterbatch
(1) Graphene surface modification: pouring 100g of graphene into 100mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min to form a uniform graphene-ethanol dispersion liquid, dropwise adding hydrochloric acid to adjust the pH to 3.2-3.8, continuously dropwise adding 0.1g of silane coupling agent, stirring and reacting for 5h in a constant-temperature water bath at 50 ℃, centrifugally separating out solid, washing the obtained solid to be neutral by using deionized water, and drying to obtain modified graphene;
(2) mixing the mixed components containing the modified graphene and the chloroprene rubber in the step (1) to form modified graphene-chloroprene rubber, wherein the weight ratio of the chloroprene rubber to the modified graphene is 25: 1;
(3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber, wherein the weight ratio of the nitrile rubber to the unmodified graphene is 50: 1;
(4) respectively thinning and passing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) for 5 times, then mixing in an internal mixer according to the weight ratio of 3:1, wherein the mixing temperature is 55 ℃, the rotating speed of the internal mixer is 100r/min, mixing for 10min, and curing and crushing to form particles to obtain the graphene rubber master batch.
Weighing 20 parts of graphene rubber master batch, 40 parts of chloroprene rubber, 30 parts of nitrile rubber, 9 parts of silicone resin, 5 parts of zinc oxide, 1.2 parts of anti-aging agent, 1.2 parts of sulfur powder, 6 parts of dioctyl sebacate, 1.0 part of accelerator NS and 1.2 parts of accelerator DM according to parts by weight; mixing the chloroprene rubber and the nitrile rubber in parts by weight at 35 ℃ for 4 min; then adding the graphene rubber master batch, the silicone resin, the zinc oxide, the anti-aging agent and the dioctyl sebacate in parts by weight, and mixing for 3min at 100 ℃; and finally adding the sulfur powder, the accelerator NS and the accelerator MD in parts by weight, thinly passing for 5 times at 130 ℃, and discharging to prepare the composite rubber material.
Example 2 preparation method of graphene rubber masterbatch
(1) Graphene surface modification: pouring 100g of graphene into 100mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min to form a uniform graphene-ethanol dispersion liquid, dropwise adding hydrochloric acid to adjust the pH to 3.2-3.8, continuously dropwise adding 0.1g of silane coupling agent, stirring and reacting for 5h in a constant-temperature water bath at 50 ℃, centrifugally separating out solid, washing the obtained solid to be neutral by using deionized water, and drying to obtain modified graphene;
(2) mixing the mixed components containing the modified graphene and the chloroprene rubber in the step (1) to form modified graphene-chloroprene rubber, wherein the weight ratio of the chloroprene rubber to the modified graphene is 10: 1;
(3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber, wherein the weight ratio of the nitrile rubber to the unmodified graphene is 30: 1;
(4) respectively thinning and passing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) for 5 times, then mixing in an internal mixer according to the weight ratio of 15:1, wherein the mixing temperature is 35 ℃, the rotating speed of the internal mixer is 100r/min, mixing for 10min, and curing and crushing to form particles to obtain the graphene rubber master batch.
Further, the graphene rubber master batch obtained in the step (4) is prepared into a composite rubber material according to the method of the embodiment 1.
Example 3 preparation method of graphene rubber masterbatch
(1) Graphene surface modification: pouring 100g of graphene into 100mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min to form a uniform graphene-ethanol dispersion liquid, dropwise adding hydrochloric acid to adjust the pH to 3.2-3.8, continuously dropwise adding 0.1g of silane coupling agent, stirring and reacting for 5h in a constant-temperature water bath at 50 ℃, centrifugally separating out solid, washing the obtained solid to be neutral by using deionized water, and drying to obtain modified graphene;
(2) mixing the mixed components containing the modified graphene and the chloroprene rubber in the step (1) to form modified graphene-chloroprene rubber, wherein the weight ratio of the chloroprene rubber to the modified graphene is 15: 1;
(3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber, wherein the weight ratio of the nitrile rubber to the unmodified graphene is 40: 1;
(4) respectively thinning and passing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) for 5 times, then putting the materials into an internal mixer according to the weight ratio of 10:1, mixing for 10min at the mixing temperature of 45 ℃ and the rotating speed of the internal mixer of 100r/min, and curing and crushing to form particles to obtain the graphene rubber master batch.
Further, the graphene rubber master batch obtained in the step (4) is prepared into a composite rubber material according to the method of the embodiment 1.
Comparative example 1 preparation method of graphene rubber master batch
The only difference from example 3 is that the weight ratio of the modified graphene-chloroprene rubber and the graphene-nitrile rubber used in step (4) is 1: 1.
Comparative example 2 preparation method of graphene rubber masterbatch
The only difference from example 3 is that the unmodified graphene in step (3) was replaced by an equivalent amount of the modified graphene prepared in step (1).
Comparative example 3 preparation method of graphene rubber master batch
The difference from example 3 is only that the addition of the graphene rubber master batch is omitted during the preparation of the rubber composite.
Experimental example 1 mechanical Properties of rubber composite Material
The rubber composites prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to mechanical property tests in accordance with GB/T528-2009, and the test results are shown in Table 1.
TABLE 1
Comparing the experimental data of examples 1 to 3 and comparative example 3 in table 1, it can be found that the graphene rubber masterbatch prepared according to the present invention can significantly improve the tensile properties of the rubber composite material, and specifically, can simultaneously increase the tensile strength and the elongation at break of the rubber composite material. Comparing the experimental data of example 3 and comparative example 1, it can be found that the weight ratio of the modified graphene-chloroprene rubber and the graphene-nitrile rubber in the masterbatch can affect the efficacy of the graphene masterbatch in improving the performance of the rubber composite, and when the weight ratio of the modified graphene-chloroprene rubber and the graphene-nitrile rubber exceeds the range of 15-2:1, the efficacy of the graphene rubber masterbatch in improving the performance of the rubber composite can be reduced. Comparing example 3 with comparative example 2, when the graphene in the graphene-nitrile rubber is replaced by the modified graphene, the tensile strength and the elongation at break of the rubber composite material are both reduced.
Claims (5)
1. The preparation method of the graphene rubber master batch is characterized by comprising the following steps:
(1) carrying out modification treatment on graphene, pouring 100g of graphene into 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min to form uniform graphene-ethanol dispersion liquid, dropwise adding hydrochloric acid to adjust the pH value to 3.2-3.8, continuously dropwise adding 0.1g of silane coupling agent, stirring and reacting for 5h in a constant-temperature water bath at 50 ℃, centrifugally separating out solids, cleaning and drying;
(2) mixing the mixed components containing the modified graphene in the step (1) and chloroprene rubber to form modified graphene-chloroprene rubber, wherein the weight ratio of the chloroprene rubber to the modified graphene is 25-10: 1;
(3) mixing a mixture containing unmodified graphene and nitrile rubber to form graphene-nitrile rubber, wherein the weight ratio of the nitrile rubber to the graphene is 50-30: 1;
(4) and (3) mixing the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) according to a weight ratio of 15-3:1, and curing and crushing to form particles to obtain the graphene rubber master batch.
2. The preparation method according to claim 1, wherein in the step (4), the modified graphene-chloroprene rubber obtained in the step (2) and the graphene-nitrile rubber obtained in the step (3) are respectively passed through a thin tube for 5 times, and then are put into an internal mixer to be mixed uniformly, wherein the mixing temperature is 35-55 ℃, the rotating speed of the internal mixer is 60-100r/min, and the mixing time is 10-40 min.
3. The preparation method according to claim 2, wherein the mixing temperature of the modified graphene-chloroprene rubber and the graphene-nitrile rubber in the step (4) is 50 ℃.
4. The graphene rubber master batch prepared according to the preparation method of claim 1.
5. Use of the graphene rubber masterbatch according to claim 4 in the preparation of a rubber material.
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