CN106589460A - Rubber chemical reduced and modified graphene oxide as well as preparation method and application thereof - Google Patents

Rubber chemical reduced and modified graphene oxide as well as preparation method and application thereof Download PDF

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CN106589460A
CN106589460A CN201611148962.7A CN201611148962A CN106589460A CN 106589460 A CN106589460 A CN 106589460A CN 201611148962 A CN201611148962 A CN 201611148962A CN 106589460 A CN106589460 A CN 106589460A
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rubber
graphene
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graphene oxide
rubber chemicals
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CN106589460B (en
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贾志欣
钟邦超
董焕焕
林静
罗远芳
贾德民
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South China University of Technology SCUT
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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Abstract

The invention discloses rubber chemical reduced and modified graphene oxide as well as a preparation method and an application thereof. The graphene oxide can be simultaneously reduced and modified just by conducting a reaction in one step; and specifically, the rubber chemical modified graphene is prepared by the following steps: mixing graphite oxide and water, and conducting ultrasonic exfoliation so as to obtain graphene oxide water dispersion liquid; mixing a rubber chemical solution with the graphene oxide water dispersion liquid, and conducting heating and stirring so as to obtain the rubber chemical modified graphene. According to the invention, a reducing agent is non-toxic and environment-friendly, the method is simple and easy to implement and reaction conditions are mild; and the prepared graphene is low in content of an oxygen-containing functional group in surface and high in conjugation degree; some rubber chemicals are chemically grafted on the surface of the graphene, so that the uniform dispersion of the graphene in rubber is promoted and an interface bonding action between the graphene and the rubber matrix is enhanced, and in addition, the migration and volatilization of the rubber chemicals are prevented and the action efficiency of the rubber chemicals is improved, so that the performance of a rubber/graphene composite material is improved. The invention provides a new opportunity and a new way for the green mass preparation of the graphene and for the preparation of the high-performance rubber/graphene nano composite material.

Description

A kind of rubber chemicals reduction and modified graphene oxide and preparation method and application
Technical field
The invention belongs to field of material preparation, and in particular to a kind of rubber chemicals reduction and modified graphene oxide and its system Preparation Method and application.
Background technology
Graphene is latest development and the nano material with revolutionary significance, is found first in 2004, is a kind of By the two-dimentional conjugated structure of monolayer carbon atomic building, the characteristic such as the mechanics with superelevation and fabulous heat conduction, conduction.It is only based on its The chemical constitution and excellent combination property of spy, Graphene is caused widely in fields such as new forms of energy, biotechnology, new materials Concern.Graphene is usually to be obtained through reduction by graphene oxide, and its main preparation method has chemical reduction method, solvent heat Reducing process, chemical meteorology deposition method, photo-reduction etc..Wherein, chemical reduction method due to can magnanimity prepare, and technique letter Single, cost is relatively low, thus all receives high praise especially in basic research and industrial application.Currently, chemical reduction method institute Using reducing agent be mainly hydrazine hydrate.However, hydrazine hydrate toxicity is big, and blast is susceptible to when using in a large number.So, Using nontoxic, environmentally friendly reducing agent, one class process is simple of exploitation, reaction condition are gentle, the Graphene of low cost is very necessary , with significant theoretical and practical significance.
Rubber is the indispensable strategic goods and materials of country, is that national economy, new and high technology and defence and military field can not The critical material of replacement.But the intensity and elasticity of rubber raw rubber are undesirable, it is necessary to add reinforced filling and accelerator, age resistor etc. Various auxiliary agents just have use value.The performance developed rapidly with industrial economy transition and upgrade to rubber of current China's national defense military project Put forward higher requirement, the filler such as conventional carbon black, white carbon is difficult to meet use requirement.Graphene should as Nano filling In rubber composite, it is expected to significantly improve the performances such as the mechanics of material, thermal conductivity, Dynamic Viscoelastic, with wide Development prospect.However, because Graphene is difficult to be uniformly dispersed in rubber, and weak, its unique advantage hardly possible is combined with rubber interface To play.To solve an above difficult problem, mainly by additional organic matter Graphene is modified to improve it in rubber so far Dispersion and interface cohesion, but modified technique is complicated, and high cost, pollution is big, DeGrain.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of process is simple, reaction condition are gentle, cost Low, free of contamination rubber chemicals reduction and the preparation method of modified graphene oxide, additionally provide a kind of surface oxygen functional group Low, conjugated degree is high, homodisperse rubber chemicals reduction and modified graphene oxide and its multiple in rubber in organic solvent Application technology in condensation material.
To solve above-mentioned technical problem, the present invention provides technical scheme below.
A kind of rubber chemicals reduction and the preparation method of modified graphene oxide, comprise the steps:
(1)Graphite oxide is mixed with water, ultrasound is peeled off, and obtains graphene oxide aqueous dispersions;
(2)During rubber chemicals are dissolved in into organic solvent or water, rubber chemicals solution is formed;
(3)Rubber chemicals solution is mixed with graphene oxide aqueous dispersions, the stirring reaction at 50 ~ 100 DEG C;
(4)By step(3)Gained product washing, vacuum drying, obtain final product rubber chemicals modified graphene.
Preferably, step(1)The concentration of the graphene oxide aqueous dispersions is 0.5 ~ 1.5mg/ml.
Preferably, step(2)The rubber chemicals are N cyclohexyl 2 benzothiazole sulfenamide(Accelerant CZ)、N- The tert-butyl group -2-[4-morpholinodithio sulfenamide(Accelerator NS), diphenylguanidine and its derivative(Such as diphenylguanidine), sub- second epithio urea and Its derivative(Such as accelerant N A22), N, N'- diphenyl trimethylene diamines(Antioxidant D PD), N- cyclohexyl-P-nethoxyaniline (Age resistor CMA), 2,6- di-tert-butyl -4- methylphenols(Antioxidant 264), 2,2' methylene bis-(4- methyl-6-tert butyl Phenol)(Antioxidant 2246), 2,2'- thiobis (4- methyl-6-tert-butylphenols)(Antioxidant 2246 S), 2,2,4- trimethyls- 1,2- dihyaroquinoline condensates(Anti-aging agent RD)With 2- dihyaroquinolines(Antioxidant A W)In one kind.
Preferably, step(2)The organic solvent is methyl alcohol, ethanol, toluene, benzene, dimethylbenzene, acetone, ether and chloroform In one or more mixed solvents.
Preferably, step(2)The quality of the rubber chemicals is 0.3 ~ 3 times of graphite oxide quality, more preferably 0.75 ~ 2.5 times.
Preferably, step(2)The concentration of the rubber chemicals solution is 1 ~ 10 mg/ml, more preferably 5 ~ 9 mg/ ml。
Preferably, step(3)The time of the reaction is 2 ~ 7 hours, more preferably 3 ~ 6.5 hours.
Preferably, step(3)The temperature of the reaction is 55 ~ 90 DEG C, more preferably 60-75 DEG C.
Preferably, step(4)The vacuum drying temperature is 50 ~ 60 DEG C.
A kind of rubber chemicals reduction and modified graphene oxide, the rubber chemicals by obtained in above-described preparation method Reduction and modified graphene oxide are applied to prepare in rubber composite.
Preferably, the rubber chemicals reduction is with modified graphene oxide is in the list glue such as natural rubber and butadiene-styrene rubber and is used in combination Application in glue.
The present invention prepare rubber chemicals reduction and modified graphene oxide can be applicable to natural rubber, synthetic rubber and In blend compounds, rubber is had significant reinforcement, promote sulfuration, improve it is ageing-resistant, improve heat conduction, conduction etc. effect, can strengthen Interfacial interaction between rubber and Graphene, reduces rubber product(Such as tire)Rolling resistance, while improve anti-slippery, Have broad application prospects in the Rubber Industries such as green tire.
Compared with prior art, the invention has the advantages that:
(1)The invention provides a kind of preparation method using nontoxic rubber chemicals as the Graphene of reducing agent, with reaction The features such as mild condition, short reaction time.The rubber chemicals modified graphene surface oxygen functional group that obtained is low, conjugated degree Height, it is structurally consummate.
(2)Partial rubber auxiliary agent in the present invention as reducing agent can be supported on Graphene by covalent bond or non-covalent bond Surface, realizes the surface organic modification to Graphene, so as to significantly improve modified graphene dispersiveness in organic solvent Energy;Additionally, rubber chemicals are supported on after graphenic surface, its migration can be avoided and volatilized, so as to reduce the thing of rubber chemicals Reason loss, improves its functioning efficiency, and mitigates the pollution to environment.
(3)The rubber chemicals that the present invention is obtained are reduced and modified graphene oxide is due to have passed through surface organic modification, its Dispersity in rubber is uniform, and the interface cohesion between rubber strengthens, such that it is able to significantly improve rubber composite The performance such as heat conduction, conduction, mechanics, Dynamic Viscoelastic;Meanwhile, rubber chemicals modified graphene can also effectively facilitate the vulcanization of rubber and Elastomeric material ageing-resistant performance is improved, high-performance, multi-functional feature is embodied.
(4)Rubber chemicals reduction and the preparation process is simple of modified graphene oxide that the present invention is provided, are conducive to protection Environment, reduces cost and realizes industrial applications.
Description of the drawings
Fig. 1 is the FTIR spectrograms of GO, HH-G and CZ-G.
Fig. 2 a, Fig. 2 b, Fig. 2 c are respectively the C1s high-resolution XPS spectrum figures of GO, HH-G and CZ-G.
Fig. 3 is the thermogravimetric curve figure of GO, HH-G, CZ-G and CZ.
Fig. 4 a, Fig. 4 b are respectively the TEM photos of SBR/HH-G and SBR/CZ-G rubber composites.
Specific embodiment
Below in conjunction with example and accompanying drawing to the present invention be embodied as be further described, but embodiments of the present invention Not limited to this.
Embodiment 1
300mg graphite oxides are distributed in 300ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 600mg thiofide N cyclohexyl 2 benzothiazole sulfenamides(Accelerant CZ)It is dissolved in the anhydrous second of 120ml In alcohol, and it is added in above-mentioned GO aqueous dispersions, stirring reaction 3 hours at 90 DEG C, product is put into Jing after ethanol washing In vacuum drying oven, it is dried to constant weight at 50 DEG C, is promoted agent CZ modified graphenes(CZ-G).In order to this is better described Bright characteristic, by existing conventional method the Graphene of hydrazine hydrate reduction is prepared for, and is named as HH-G, to compare.
The infrared spectrogram of CZ-G, HH-G and GO manufactured in the present embodiment(FTIR)As shown in Figure 1.As seen from the figure, contrast The FTIR spectrograms of GO, the spectrogram of CZ-G and HH-G is in 1729 cm-1、1418 cm-1、1226 cm-1、1056 cm-1The oxygen-containing official at place Absworption peak can be rolled into a ball and substantially weaken even disappearance, this explanation CZ can effectively reduce GO, and its reduction effect is suitable with hydrazine hydrate.This Outward, methylene is occurred in that in the spectrogram of CZ-G(2941 cm-1、2858 cm-1), C-N and C-S(1100~1350 cm-1Near)'s Characteristic peak, this explanation CZ has been supported on the surface of Graphene by chemical action.Accelerant CZ can be with to the reduction effect of GO From the high-resolution x-ray photoelectron spectroscopy figure of C1s in Fig. 2 a, Fig. 2 b, Fig. 2 c(XPS)Result be confirmed.Can be with from figure It was observed that, C=O bond in GO, carbon oxygen singly-bound peak intensity it is very high, and after CZ reduction, the peak intensity of carbon and oxygen functional group Substantially weaken, suitable with the Graphene of hydrazine hydrate reduction, again illustrating CZ can effectively reduce GO.Fig. 3 is GO, HH-G, CZ- The thermogravimetric curve figure of G and CZ, shows, the mass fraction of contained CZ is about 20 % in CZ-G in figure.
With CZ-G manufactured in the present embodiment and HH-G and butadiene-styrene rubber(SBR)It is compound, prepare SBR composites(SBR/CZ- G and SBR/HH-G), its formula is as follows(Unit:phr):SBR 100;Antioxidant 4020 2;Accelerant CZ 1.2;Zinc oxide 5;Stearic acid 2;Filler(CZ-G and HH-G)4.It is pointed out that the CZ of CZ-G surface graftings needs to calculate in total promotion In agent number, to guarantee that accelerator number is identical contained by all formulas.
Fig. 4 a, Fig. 4 b are the transmission electron microscopes of two kinds of composites(TEM)Photo.It can be seen that HH-G is in rubber Occurs agglomeration in matrix;And CZ-G uniformly can be dispersed in rubber matrix with monolithic layer, this is due to surface grafting Organic additive CZ, changes the surface nature of CZ-G, caused by enhancing its compatibility with rubber matrix.Benefits of the CZ-G to SBR More preferably, tensile strength brings up to 15.1 MPa to reinforcing effect of the potent fruit than HH-G from 10.8, and tearing strength brings up to from 22.3 28.8 kN/m, conductivity percolation threshold is down to 1.6 vol% from 5.3.Additionally, Dynamic Viscoelastic performance result shows, SBR/CZ-G rubbers Glue composite has higher fissipation factor than SBR/HH-G rubber composite at 0 DEG C(tanδ)(Improve 6%), and 60 DEG C when possess relatively low tan δ values(Reduce by 16%).These results suggest that, the wet-sliding resistant performance of SBR/CZ-G rubber composites is carried Height, rolling resistance declines, and illustrates that CZ-G has a good application prospect in rubber for tire composite, can effectively reduce vapour Car oil consumption and exhaust emissions, meet the strategy of sustainable development of national " energy-saving and emission-reduction ".
Embodiment 2
200mg graphite oxides are distributed in 400ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 600mg rubber antioxidant N, N'- diphenyl trimethylene diamines(Antioxidant D PD)In being dissolved in 60ml toluene, and it is added to above-mentioned In GO aqueous dispersions, stirring reaction 2,5,8 hours under the conditions of 60 DEG C, product is put into vacuum drying oven Jing after ethanol washing In, it is dried to constant weight at 50 DEG C, obtain antioxidant D PD modified graphenes(DPD-G).
FTIR and13C nuclear-magnetism results show that the oxygen-containing functional group in DPD-G is substantially reduced compared to GO, illustrate that DPD can Effectively reduction GO.
It is combined with DPD-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be anti-old Agent 4020 is changed into beyond DPD, and remaining is same as Example 1, while ensureing that the DPD numbers contained by all formulas are identical.As a result Show, DPD-G is dispersed with monolithic layer in SBR matrixes.The tensile strength and tearing strength ratio of SBR/DPD-G composites SBR/HH-G composites are higher by respectively 1.9 MPa and 3.1 kN/m.DPD-G can also give composite excellent resistance to ag(e)ing Can, the oxidation induction period of SBR/DPD-G composites improves 6 minutes than SBR/HH-G composite.
Embodiment 3
300mg graphite oxides are distributed in 200ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 300mg rubber antioxidant N tert butyl benzothiazole 2 sulfenamides(Accelerator NS)In being dissolved in 60ml acetone, and add Enter in above-mentioned GO aqueous dispersions, stirring reaction 1 hour under the conditions of 60 DEG C, product is put into vacuum Jing after ethanol washing In baking oven, it is dried to constant weight at 60 DEG C, obtains age resistor NS modified graphenes(NS-G).
FTIR and XPS show that the oxygen-containing functional group in NS-G is substantially reduced compared to GO, illustrate that NS can be reduced effectively GO。
It is combined with NS-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed accelerator CZ is changed into beyond NS, and remaining is same as Example 1, while ensureing that the NS numbers contained by all formulas are identical.As a result show, NS-G is in NR matrixes with monolithic layer dispersion.The tensile strength and elongation at break of SBR/NS-G composites compares respectively SBR/ HH-G composites are higher by 2.8 MPa and 150%, in 60 DEG C of tan δ values than low by 10%.Meanwhile, the sulfuric of SBR/NS-G elastomeric compounds The change time shortens 4 minutes than the sulfurizing time of SBR/HH-G elastomeric compound.
Embodiment 4
500mg graphite oxides are distributed in 500ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 800mg rubber antioxidants N- cyclohexyl-P-nethoxyaniline(Age resistor CMA)In being dissolved in 100ml toluene, and it is added to In above-mentioned GO aqueous dispersions, stirring reaction 3 hours under the conditions of 50 DEG C, product is put into vacuum drying oven Jing after ethanol washing In, it is dried to constant weight at 60 DEG C, obtain age resistor CMA modified graphenes(CMA-G).
XPS and nuclear magnetic resonance13C is as a result, it was confirmed that CMA can effectively reduce GO.
It is combined with CMA-G manufactured in the present embodiment and HH-G and natural rubber (NR), prepares rubber composite, it is matched somebody with somebody In addition to antioxidant 4020 is changed into CMA, remaining is same as Example 1, while ensureing the CMA numbers contained by all formulas for side It is identical.As a result show, CMA-G can significantly improve the heatproof air aging performance of composite, the oxygen of NR/CMA-G composites Change induction period improves 7 minutes than NR/HH-G composite.
Embodiment 5
100mg graphite oxides are distributed in 100ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 150mg rubber antioxidant 2,6- di-tert-butyl -4- methylphenols(Antioxidant 264)In being dissolved in 50ml absolute ethyl alcohols, and In being added to above-mentioned GO aqueous dispersions, stirring reaction 5 hours under the conditions of 100 DEG C, product is put into true Jing after ethanol washing In empty baking oven, it is dried to constant weight at 60 DEG C, obtains the modified graphene of vulcanization accelerator 264(264-G).
FTIR and XPS show that the oxygen-containing functional group in 264-G is substantially reduced compared to GO, it was confirmed that the reduction of 264 couples of GO Ability.
It is combined with 264-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be promoted Agent 4020 is changed into beyond 264, and remaining is same as Example 1, while ensureing that 264 numbers contained by all formulas are identical.As a result Show, the tensile strength of SBR/264-G composites is higher by 3.3 MPa than the tensile strength of SBR/HH-G composite, aoxidize Induction period extends 5 minutes.
Embodiment 6
200mg graphite oxides are distributed in 200ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 330mg thiofides Asia second epithio urea(Accelerant N A22)In being dissolved in 60ml absolute ethyl alcohols, and it is added to In stating GO aqueous dispersions, stirring reaction 6 hours under the conditions of 55 DEG C, product Jing ethanol washing after, in being put into vacuum drying oven, It is dried to constant weight at 50 DEG C, obtains vulcanization accelerator NA22 modified graphenes(NA22-G).
Nuclear magnetic resonance13C and XPS show that the oxygen-containing functional group in NA22-G is substantially reduced compared to GO, illustrates accelerator NA22 can effectively reduce GO.GO and NA22-G are dispersed in water, it can be observed that, GO is dispersed in water presentation buff, And after accelerant N A22 reduction, the color of NA22-G dispersion liquids is substantially deepened, after this Graphene with hydrazine hydrate reduction Phenomenon it is consistent, further demonstrate that accelerant N A22 to the extensive of the efficient reducing power of GO and NA22-G surfaces conjugated structure It is multiple.
It is combined with NA22-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be promoted Agent CZ is changed into beyond NA22, and remaining is same as Example 1, while ensureing that the NA22 numbers contained by all formulas are identical.As a result Prove, compare HH-G, NA22-G has more preferable dispersity in SBR matrixes, and acts on the interface cohesion of rubber matrix Also it is higher.The tensile strength of SBR/NA22-G composites, tearing strength and elongation at break are respectively than SBR/HH-G composite wood Material improves 3.5 MPa, 4.6 kN/m and 100%.Dynamic viscoelasticity test result shows that SBR/NA22-G rubber composites exist 60 DEG C of tan δ values are lower than SBR/HH-G rubber composite(Reduce by 13%), it is higher in 0 DEG C of tan δ values(Improve 6%), explanation NA22-G imparts the lower rolling resistance of SBR composites and the wet-sliding resistant performance of Geng Gao, and NA22-G is in green tire row Industry has a good application prospect.
Embodiment 7
100mg graphite oxides are distributed in 200ml deionized waters, ultrasound is peeled off, form graphene oxide(GO)Moisture dissipates Liquid;By 30mg rubber antioxidant 2,2'- thiobis (4- methyl-6-tert-butylphenols)(2246S)3ml toluene is dissolved in ethanol In mixed solvent(Volume ratio is 1:1), and be added in above-mentioned GO aqueous dispersions, stirring reaction 4.5 hours under the conditions of 75 DEG C, Product in being put into vacuum drying oven, is dried to constant weight Jing after ethanol washing at 50 DEG C, obtains the modified stones of antioxidant 2246 S Black alkene(2246S-G).
Nuclear magnetic resonance FTIR,13C and XPS show that the oxygen-containing functional group in 2246S-G is substantially reduced compared to GO, illustrate anti- Old agent 2246S can effectively reduce GO.Meanwhile, thermal weight loss result shows that antioxidant 2246 S is in the percent grafting of graphenic surface 18.6wt%。
It is combined with 2246S-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be anti- Old agent 4020 is changed into beyond 2246S, and remaining is same as Example 1, while ensureing the 2246S number phases contained by all formulas Together.As a result show, 2246S-G can significantly improve the heatproof air aging performance of composite, SBR/2246S-G composites Oxidation induction period improves 8 minutes than SBR/HH-G composite.

Claims (9)

1. a kind of rubber chemicals reduce the preparation method with modified graphene oxide, it is characterised in that comprise the steps:
(1)Graphite oxide is mixed with water, ultrasound is peeled off, and obtains graphene oxide aqueous dispersions;
(2)During rubber chemicals are dissolved in into organic solvent or water, rubber chemicals solution is formed;
(3)Rubber chemicals solution is mixed with graphene oxide aqueous dispersions, the stirring reaction at 50 ~ 100 DEG C;
(4)By step(3)Gained product washing, vacuum drying, obtain final product rubber chemicals reduction and modified graphene oxide.
2. preparation method according to claim 1, it is characterised in that step(1)The graphene oxide aqueous dispersions Concentration is 0.5 ~ 1.5mg/ml.
3. preparation method according to claim 1, it is characterised in that step(2)The rubber chemicals are N- cyclohexyl -2- Benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, diphenylguanidine and its derivative, sub- second epithio urea and its Derivative, N, N'- diphenyl trimethylene diamines, N- cyclohexyl-P-nethoxyaniline, 2,6- di-tert-butyl -4- methylphenols, 2, 2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols), 2,2'- thiobis (4- methyl-6-tert-butylphenols), 2,2,4- front threes One kind in base -1,2- dihyaroquinolines condensate and 2- dihyaroquinolines.
4. preparation method according to claim 1, it is characterised in that step(2)The organic solvent be methyl alcohol, ethanol, One or more mixed solvents in toluene, benzene, dimethylbenzene, acetone, ether and chloroform.
5. preparation method according to claim 1, it is characterised in that step(2)The quality of the rubber chemicals is oxidation 0.3 ~ 3 times of graphite quality.
6. preparation method according to claim 1, it is characterised in that step(2)The concentration of the rubber chemicals solution is 1 ~10mg/ml。
7. preparation method according to claim 1, it is characterised in that step(3)The time of the reaction is 1~8 hour.
8. a kind of rubber chemicals are reduced and modified graphite oxide obtained in the preparation method by described in any one of claim 1-7 Alkene.
9. a kind of reduction of rubber chemicals and modified graphene oxide described in claim 8 is applied to prepare rubber composite In.
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CN109206664A (en) * 2017-07-04 2019-01-15 北京橡胶工业研究设计院有限公司 A kind of rubber graphene composite sulfuration promotor and preparation method thereof
CN108314014A (en) * 2018-03-14 2018-07-24 华南理工大学 A kind of reduction of thiofide and modified graphene oxide and the preparation method and application thereof
CN109021293A (en) * 2018-06-12 2018-12-18 华南理工大学 A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof
CN111718516A (en) * 2020-06-11 2020-09-29 株洲时代新材料科技股份有限公司 Preparation method and application of composite rubber filler
CN111718516B (en) * 2020-06-11 2022-04-22 株洲时代新材料科技股份有限公司 Preparation method and application of composite rubber filler
CN112408374A (en) * 2020-11-27 2021-02-26 浙江工业大学 Method for reducing graphene agglomeration

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