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 PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 86
- 239000005060 rubber Substances 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000126 substance Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract 1
- 238000004299 exfoliation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920006247 high-performance elastomer Polymers 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 7
- 229920003052 natural elastomer Polymers 0.000 description 7
- 229920001194 natural rubber Polymers 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K2201/001—Conductive additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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
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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| CN106854387A (en) * | 2017-01-04 | 2017-06-16 | 华南理工大学 | A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application |
| 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 |
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| CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
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