CN105111531A - Graphene-modified wear-resistant rubber - Google Patents
Graphene-modified wear-resistant rubber Download PDFInfo
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- CN105111531A CN105111531A CN201510208883.XA CN201510208883A CN105111531A CN 105111531 A CN105111531 A CN 105111531A CN 201510208883 A CN201510208883 A CN 201510208883A CN 105111531 A CN105111531 A CN 105111531A
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Abstract
The invention relates to a graphene-modified wear-resistant rubber. The graphene-modified wear-resistant rubber comprises, by weight, 48.9 to 56.5% of synthetic rubber, 1.5 to 2.5% of a sulfuration promoter, 8 to 18% of graphene, 25 to 30% of a filling material, 1.5 to 5% of a plasticizer and 0.1 to 3% of an auxiliary agent. According to the invention, graphene is added into the rubber so as to improve strength of the rubber, and since graphene has good lubrication effect, wear resistance of the rubber can be improved; and addition of asbestos fiber and polyimide fiber enables heat resistance of the rubber to be substantially improved.
Description
Technical field
The present invention relates to field of rubber materials, particularly relate to a kind of wear resistance improving rubber, the abrasive rubber of the Graphene modification of tensile strength.
Background technology
Rubber is the strong flexible polymer material with reversible deformation, and at room temperature high resilience can produce comparatively large deformation under very little External Force Acting, resilient after removing external force.The molecular chain of rubber can be cross-linked, and when the rubber after crosslinked deforms by External Force Acting, has the ability of restoring rapidly, and has preferably physical and mechanical property and chemical stability.Rubber is the basic raw material of rubber industry, is widely used in and manufactures tire, sebific duct, adhesive tape, cable and other various rubber items.Traditional rubber item is not weather-proof, without by, low, the easy be full of cracks of crocking resistance, poor tensile strength, such that the work-ing life of rubber item is short, cost is higher.
Geim and Novoselov of Man Chesidun university of Britain in 2004 obtains self-existent two-dimensional graphene (Gra-phene by tape stripping high starch breeding, GN), since crystal, Graphene has become one of extremely concerned study hotspot of material science.In fact Graphene is exactly the graphite of monoatomic layer, and it has unique two-dirnentional structure and excellent mechanics, thermodynamics, optics and electric property.
Graphene is at present the thinnest is in the world the hardest nano material also, and it is almost completely transparent, to the light absorbing 2.3%, thermal conductivity up to 5300W/mk, higher than carbon nanotube and diamond.Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, has intensity high, and specific surface area is large, high chemical reactivity, the feature of high fillibility.
Chinese patent publication No. CN102093607A, date of publication on June 15th, 2011, name is called a kind of high-strength high-elasticity oil resisting rubber, this application case discloses a kind of high-strength high-elasticity oil resisting rubber, is made up of hydrogenated nitrile-butadiene rubber 100 parts, thermo-stabilizer 10-20 part, softening agent 10-15 part, strengthening agent 10-25 part, vulcanizing agent 1-2 part, additional crosslinker 1-5 part, peroxide vulcanizing agent 2-5 part.Its weak point is, but rubber resistance toheat, oil resistance effect its toughness good that this formula is produced, and crocking resistance is poor.
Summary of the invention
The object of the invention is in order to solve traditional rubber item not weather-proof, without by, low, the easy be full of cracks of crocking resistance, poor tensile strength, make the work-ing life of rubber item is short, cost is higher defect and provide a kind of wear resistance improving rubber, the abrasive rubber of the Graphene modification of tensile strength.
To achieve these goals, the present invention is by the following technical solutions:
A kind of abrasive rubber of Graphene modification, comprise synthetic rubber, vulcanization accelerator, stopping composition, softening agent, described abrasive rubber also comprises Graphene and auxiliary agent, and the weight percent of each component in rubber is respectively synthetic rubber 48.9-56.5%, vulcanization accelerator 1.5-2.5%, Graphene 8-18%, stopping composition 25-30%, softening agent 1.5-5% and auxiliary agent 0.1-3%.In the technical program, Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, has intensity high, and specific surface area is large, high chemical reactivity, the feature of high fillibility; In rubber, add the intensity that Graphene improves rubber, Graphene high lubricating effect, therefore can improve the rub resistance of rubber.
As preferably, auxiliary agent is the mixture of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate.In the technical program, fibrous magnesium silicate and adding of polyimide fiber can make the thermotolerance of rubber significantly improve, and improve the toughness of rubber, improve the solidity to corrosion of rubber, the crocking resistance of rubber is increased; Nano titanium oxide has the advantages such as good photocatalytic activity, chemical stability, thermostability, non-secondary pollution, safety non-toxic, just can catalytic decomposition bacterium and pollutent under the condition of natural light irradiation, long-term existence has excellent environment friendly in physical environment, N, N-diethylethanolamine makes Graphene, and in system, dispersiveness is better and more even.
As preferably, the mass ratio of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate is 1:2:1-3:1-5.
As preferably, Graphene be size distribution in the black powder of 10 nanometer-100 microns, be the carbonaceous material being paralleled by individual layer-1000 layers or form close to parallel graphene sheet layer, specific surface area is 50-1500 ㎡/g.
As preferably, in described Graphene, carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
As preferably, synthetic rubber is selected from one or more in paracril, silicon rubber, cis-1,4-polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), chloroprene rubber, and stopping composition is selected from one or more in carbon black, calcium carbonate, barium sulfate, zinc sulfate, titanium dioxide, talcum powder.
As preferably, described Graphene also includes the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
As preferably, Graphene before addition, at magneticstrength 5000-5250GS, ultrasonic disperse 30-45min under Ultrasonic Conditions simultaneously.
The invention has the beneficial effects as follows, in rubber, add the intensity that Graphene improves rubber, Graphene high lubricating effect, therefore can improve the rub resistance of rubber; Fibrous magnesium silicate and adding of polyimide fiber can make the thermotolerance of rubber significantly improve.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained:
In the present invention, if not refer in particular to, the raw material adopted all can be buied from market or this area is conventional, and the method in following embodiment, if no special instructions, is the ordinary method of this area.
Raw material needed for the rubber related in the present invention is marketable material, wherein, synthetic rubber is selected from paracril, silicon rubber, cis-1,4-polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), one or more in chloroprene rubber, stopping composition is selected from carbon black, calcium carbonate, barium sulfate, zinc sulfate, titanium dioxide, one or more in talcum powder, stopping composition can also be the rhombspar of containing magnesium sulfate, containing the wollastonite of Calucium Silicate powder, the barite of containing sulfate, gypsum, stone containing indefiniteness charcoal is black, coal dust and other siliceous konilites (diatomite), asbestos, agalmatolite, coal gangue, resinous shale etc., vulcanization accelerator is nano zine oxide or sulphur, softening agent is purchased from Huainan Rui Ying environment-friendly materials company limited.
The Ao Shen novel material limited liability company of Lianyungang, polyimide fiber hook Jiangsu Province; Fibrous magnesium silicate builds Feng Baowen friction materials company limited purchased from Laiyuan.
Graphene raw material, Graphene powder, Graphene slurry are commercially available, purchased from Ningbo Mo Xi Science and Technology Ltd..
Graphene be size distribution in the black powder of 10 nanometer-100 microns, be the carbonaceous material being paralleled by individual layer-1000 layers or form close to parallel graphene sheet layer, specific surface area is 50-1500 ㎡/g; Carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
Graphene also can include the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
Embodiment 1
Photocatalyst titanium dioxide, N, N-diethylethanolamine, polyimide fiber and fibrous magnesium silicate are first mixed with acetone, at 60 DEG C, processes 8h, then centrifugation oven dry at 135 DEG C; Then graphene powder and auxiliary agent are added in the raw material of rubber and mix the rear rubber preparing Graphene modification according to the existing technique preparing rubber.Wherein paracril 56.5%, softening agent 5%, stopping composition carbon black, calcium carbonate and barium sulfate 25%, vulcanization accelerator sulphur and nano zine oxide 2.5%, Graphene 8% and auxiliary agent 3%, the mass ratio of carbon black, calcium carbonate and barium sulfate is 1:1:1, the mass ratio of sulphur and nano zine oxide is 1:1, the mass ratio of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate is 1:2:1:1.
Wherein, Graphene before addition, at magneticstrength 5000GS, simultaneously ultrasonic disperse 30min under Ultrasonic Conditions.
Embodiment 2
Photocatalyst titanium dioxide, N, N-diethylethanolamine, polyimide fiber and fibrous magnesium silicate are first mixed with acetone, at 75 DEG C, processes 3h, then centrifugation oven dry at 135 DEG C; Then graphene powder and auxiliary agent are added in the raw material of rubber and mix the rear rubber preparing Graphene modification according to the existing technique preparing rubber.Wherein cis-1,4-polybutadiene rubber 52.2%, softening agent 3%, stopping composition zinc sulfate, barium sulfate and talcum powder 28%, vulcanization accelerator sulphur and nano zine oxide 1%, Graphene 14% and auxiliary agent 1.8%, zinc sulfate, barium sulfate and talcous mass ratio are 1:1:1, the mass ratio of sulphur and nano zine oxide is 1:1, the mass ratio of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate is 1:2:2:3.
Wherein, Graphene before addition, at magneticstrength 5140GS, simultaneously ultrasonic disperse 35min under Ultrasonic Conditions.
Embodiment 3
Polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate are first mixed with acetone, at 65 DEG C, processes 5h, then centrifugation oven dry at 135 DEG C; Then graphene powder and auxiliary agent are added in the raw material of rubber and mix the rear rubber preparing Graphene modification according to the existing technique preparing rubber.Wherein styrene-butadiene rubber(SBR) 48.9%, softening agent 1.5%, stopping composition carbon black, calcium carbonate and barium sulfate 30%, vulcanization accelerator sulphur and nano zine oxide 1.5%, Graphene 18% and auxiliary agent 0.1%, the mass ratio of carbon black, calcium carbonate and barium sulfate is that the mass ratio of 1:1.5:2, sulphur and nano zine oxide is 1:2, the mass ratio of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate is 1:2:1:3.
Wherein, Graphene before addition, at magneticstrength 5250GS, simultaneously ultrasonic disperse 45min under Ultrasonic Conditions.
Comparative example 1, commercially available rubber, purchased from Osaka, Shenzhen Vistavision rubber item company limited.
Comparative example 2, formula used is identical with embodiment 1 with method for making, and unique difference does not wherein add Graphene.
The rubber obtained by embodiment 1-3 and the rubber of comparative example 1-2 are tested, and result is as follows:
Table 1, test result
| Wear resistance | Tensile strength/MPa | |
| Embodiment 1 | Excellent | 35 |
| Embodiment 2 | Excellent | 37 |
| Embodiment 3 | Excellent | 41 |
| Comparative example 1 | Good | 21 |
| Comparative example 2 | Good | 27.8 |
From table 1, the tensile strength of the Graphene modified rubber that the present invention is worth obviously is better than the rubber of comparative example 1-2, and in rubber, add the intensity that Graphene improves rubber, Graphene high lubricating effect, therefore can improve the rub resistance of rubber; Fibrous magnesium silicate and adding of polyimide fiber can make the thermotolerance of rubber significantly improve, and improve the solidity to corrosion of rubber, the crocking resistance of rubber is increased.
Above-described embodiment is a kind of preferred version of the present invention, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (8)
1. the abrasive rubber of a Graphene modification, comprise synthetic rubber, vulcanization accelerator, stopping composition, softening agent, it is characterized in that, described abrasive rubber also comprises Graphene and auxiliary agent, and the weight percent of each component in rubber is respectively synthetic rubber 48.9-56.5%, vulcanization accelerator 1.5-2.5%, Graphene 8-18%, stopping composition 25-30%, softening agent 1.5-5% and auxiliary agent 0.1-3%.
2. the abrasive rubber of a kind of Graphene modification according to claim 1, is characterized in that, auxiliary agent is the mixture of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate.
3. the abrasive rubber of a kind of Graphene modification according to claim 2, is characterized in that, the mass ratio of polyimide fiber, N, N-diethylethanolamine, photocatalyst titanium dioxide and fibrous magnesium silicate is 1:2:1-3:1-5.
4. the abrasive rubber of a kind of Graphene modification according to claim 1, it is characterized in that, Graphene is that size distribution is in the black powder of 10 nanometer-100 microns, be the carbonaceous material being paralleled by individual layer-1000 layers or form close to parallel graphene sheet layer, specific surface area is 50-1500 ㎡/g.
5. the abrasive rubber of a kind of Graphene modification according to claim 1 or 4, is characterized in that, in described Graphene, carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
6. the abrasive rubber of a kind of Graphene modification according to claim 1, it is characterized in that, synthetic rubber is selected from one or more in paracril, silicon rubber, cis-1,4-polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), chloroprene rubber, and stopping composition is selected from one or more in carbon black, calcium carbonate, barium sulfate, zinc sulfate, titanium dioxide, talcum powder.
7. the abrasive rubber of a kind of Graphene modification according to claim 1 or 4, it is characterized in that, described Graphene also includes the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
8. the abrasive rubber of a kind of Graphene modification according to claim 1 or 4, is characterized in that, Graphene before addition, at magneticstrength 5000-5250GS, simultaneously ultrasonic disperse 30-45min under Ultrasonic Conditions.
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| CN105400024A (en) * | 2015-12-10 | 2016-03-16 | 北京化工大学 | High-wear-resistance chloroprene rubber |
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| CN109135298A (en) * | 2018-09-08 | 2019-01-04 | 佛山朝鸿新材料科技有限公司 | A kind of wear-resisting hydrophobic type semiconductor silicon rubber |
| CN111218068A (en) * | 2019-04-23 | 2020-06-02 | 烟台桑尼橡胶有限公司 | Formula and preparation process of graphene-containing high-wear-resistance rubber dam and gas shield dam |
| CN110256743A (en) * | 2019-05-27 | 2019-09-20 | 常州暖乐康碳材料科技有限公司 | Antistatic, the wear-resisting graphene-based rubber of tire |
| CN110628140A (en) * | 2019-10-15 | 2019-12-31 | 福建宸琦新材料科技有限公司 | Wear-resistant runway granular material and preparation method thereof |
| CN110965834A (en) * | 2019-11-01 | 2020-04-07 | 中国建筑股份有限公司 | Graphene-based shock insulation support and construction method thereof |
| CN110965834B (en) * | 2019-11-01 | 2023-01-03 | 中国建筑股份有限公司 | Graphene-based shock insulation support and construction method thereof |
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| CN105111531B (en) | 2017-01-25 |
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