CN108314014A - A kind of reduction of thiofide and modified graphene oxide and the preparation method and application thereof - Google Patents
A kind of reduction of thiofide and modified graphene oxide and the preparation method and application thereof Download PDFInfo
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- CN108314014A CN108314014A CN201810207294.3A CN201810207294A CN108314014A CN 108314014 A CN108314014 A CN 108314014A CN 201810207294 A CN201810207294 A CN 201810207294A CN 108314014 A CN108314014 A CN 108314014A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of reduction of thiofide and modified graphene oxides and the preparation method and application thereof.This method first mixes graphite oxide with deionized water, ultrasound stripping is distributed in water, then rubber accelerator solution is mixed with graphene oxide water solution, heating stirring, washed, extracting, drying, thiofide reduction and modified graphene oxide are obtained, and thiofide reduction and modified graphene oxide are added in rubber.Graphene surface chemical graft after the reduction has accelerating agent, it can prevent the stacking of graphene film interlayer, it is avoided that accelerating agent migrates volatilization in rubber matrix as caused by " bloom " effect again, the interface interaction between hydridization filler dispersity in a polymer matrix and polymer graphite alkene is significantly improved, so as to improve the comprehensive performance of rubber/graphene composite material.Therefore, the present invention all has potential application value in the preparation field of functionalization filler and high-performance composite materials.
Description
Technical field
The present invention relates to rubber materials, and in particular to a kind of reduction of thiofide and modified graphene oxide and its
Preparation method and application.
Background technology
Graphene（Graphene）It is a kind of two dimension that hexangle type being formed in honeycomb lattice with sp2 hybridized orbits by carbon atom
Carbon nanomaterial.The performances such as mechanics and fabulous heat conduction, conduction with superelevation.Graphene has excellent optics, electricity, power
Characteristic is learned, it is with important application prospects in materialogy, micro-nano technology, the energy, biomedicine and drug delivery etc., recognized
To be a kind of future revolutionary material.The main preparation method of graphene has oxidation-reduction method, mechanical stripping method, solvent heat also
Former method, photo-reduction, SiC epitaxial growth methods etc..Wherein, oxidation-reduction method is most to have since simple for process, cost is relatively low
Realization is hoped to prepare one of method of graphene on a large scale.But the currently used reducing agent of oxidation-reduction method is predominantly hydrated
Hydrazine, hydrazine hydrate toxicity is big, and is easy to happen explosion.So it is simple for process in guarantee, under the premise of reaction condition is mild, exploitation
Nontoxic, environmentally friendly reducing agent is just particularly important.
Rubber as the indispensable strategic goods and materials of country, be national economy, new and high technology and defence and military field not
Alternative critical material.However, the intensity of rubber raw rubber and elasticity are undesirable, it is necessary to reinforced filling and various rubber be added
Auxiliary agent can improve the comprehensive performance of rubber, obtain use value.The rapid development of current China's national defense military project and industry warp
Helping, more stringent requirements are proposed for performance of the transition and upgrade to rubber, and the fillers such as common carbon black, white carbon, which are difficult to meet use, to be wanted
It asks.Graphene is applied as Nano filling in rubber composite material, is expected to significantly improve the mechanics of material, heat conduction, conduction, be moved
The performances such as state viscoelastic have vast potential for future development.However, since graphene is difficult to be uniformly dispersed in rubber, and and rubber
Interface cohesion is weak, and unique advantage is difficult to play.To solve above problem, so far mainly by additional organic matter to graphene into
Row is modified to improve its dispersion and interface cohesion in rubber, but modified technique is complicated, of high cost, pollution is big and effect is unknown
It is aobvious.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of simple for process, reaction conditions mildly, cost
The preparation method of low, free of contamination rubber accelerator reduction and modified graphene oxide, additionally provide a kind of oxygen-containing functional group it is low,
High, the evenly dispersed in organic solvent rubber accelerator of conjugated degree synchronizes reduction and modified graphene oxide and its in rubber
Application technology in composite material.
In order to solve the above technical problems, the present invention provides following technical scheme.
A kind of thiofide synchronizes the preparation method of reduction and modified graphene oxide, includes the following steps：
（1）Graphite oxide is added to the water, ultrasound stripping dispersion obtains the aqueous dispersions of graphene oxide；
（2）Rubber accelerator is dissolved in organic solvent or water, rubber accelerator solution is formed；
（3）At 30 ~ 80 DEG C, rubber accelerator solution is mixed with the aqueous dispersions of graphene oxide, is stirred to react；
（4）By step（3）Products therefrom washing is dried to get thiofide reduction and modified graphene oxide.
Preferably, step（1）The graphene oxide is prepared using existing modified Hummer methods.
Preferably, step（1）A concentration of 0.5 ~ 1.5 mg/ml of the graphene oxide dispersion.
Preferably, step（2）The rubber accelerator is 2-mercaptobenzothiazole（M）, zinc 2-mercaptobenzothiazole
Salt（MZ）, ethylene thiourea（ETU）, N, N '-diethyl thioureas（DETU）, diphenylguanidine（D）, two o-methyl-benzene guanidines（DOTG）In
It is a kind of.
Preferably, step（2）Described in organic solvent be methanol, ethyl alcohol, toluene, benzene, dimethylbenzene, acetone, ether and chlorine
One or more of imitative mixed solvent.
Preferably, step（2）The quality of the rubber accelerator is 0.5 ~ 3 times of graphite oxide quality, further preferably
For 0.8 ~ 2.5 times, most preferably 1-2 times.
Preferably, step（2）A concentration of 5 ~ 15 mg/ml of the rubber accelerator solution, further preferably 6 ~ 12
mg/ml。
Preferably, step（3）The time being stirred to react is 2-8 hours, further preferably 3-7 hours.
Preferably, step（3）The temperature of the reaction is 30 ~ 80 DEG C, further preferably 35 ~ 75 DEG C.
Preferably, step（4）The vacuum drying temperature is 50-60 DEG C.
A kind of reduction of rubber accelerator and modified graphene oxide, the rubber accelerator made from the process described above
Reduction and modified graphene oxide are applied to prepare in rubber composite material.
Preferably, rubber accelerator reduction and modified graphene oxide are in single glue such as natural rubber and butadiene-styrene rubber and simultaneously
With the application in glue.
Rubber accelerator prepared by present invention reduction and modified graphene oxide can be applied to natural rubber, synthetic rubber with
And in blend compounds, has the effects that significant reinforcement to rubber, promotes vulcanization, improvement heat conduction, conduction, rubber and graphite can be enhanced
Interfacial interaction between alkene improves the curability of rubber composite material, reduces the rolling resistance of rubber product such as tire, together
Shi Tigao anti-slippery has broad application prospects in the Rubber Industries such as green tire.
Compared with prior art, the present invention has the advantage that and characteristic：
（1）The preparation method for the graphene that the present invention provides a kind of using nontoxic rubber accelerator as reducing agent has anti-
Answer mild condition, the advantages that reaction time is short.The thiofide reduction obtained and modified graphene oxide surface contain
Oxygen functional group is low, conjugated degree is high, structurally consummate.
（2）In the present invention graphite can be supported on as the partial rubber accelerating agent of reducing agent by covalent bond or non-covalent bond
Alkene surface realizes the surface organic modification to graphene, to significantly improve dispersion of the graphene in rubber；In addition, rubber
After promoter for rubber load on the surface of graphene, its migration and volatilization are can avoid, to reduce the Physical Loss or Damage of rubber chemicals, is carried
Its high functioning efficiency, and mitigate the pollution to environment.
（3）Due to have passed through, surface is organic to be changed with modified graphene oxide for the thiofide reduction that the present invention obtains
Property, the dispersity in rubber is uniform, the interface cohesion enhancing between rubber, compound so as to significantly improve rubber
The performances such as curability, conduction, mechanics, the Dynamic Viscoelastic of material embody high-performance, multi-functional feature.
（4）The preparation process of thiofide reduction provided by the invention and modified graphene oxide is simple, favorably
In environmental protection, reduces cost and realize industrial applications.
Description of the drawings
Fig. 1 is the FTIR spectrograms of GO and M-G.
Fig. 2 a are the C1s high-resolution XPS spectrum figures of GO.
Fig. 2 b are the C1s high-resolution XPS spectrum figures of M-G.
Fig. 3 is the thermogravimetric curve figure of GO and M-G.
Fig. 4 a are the TEM photos of M-G.
Fig. 4 b are the EDS element sulphur distribution maps of M-G.
Specific implementation mode
In order to preferably describe and understand the present invention, with reference to embodiment and attached drawing, the invention will be further described,
But the scope of protection of present invention is not limited to the range of embodiment statement.
Embodiment 1
300mg graphite oxides are distributed in 300ml deionized waters, ultrasound stripping forms graphene oxide（GO）It is water-dispersed
Liquid；By 525mg rubber accelerator 2-mercaptobenzothiazoles（Captax）It is dissolved in 52.5ml acetone, and is added to above-mentioned oxidation
In the aqueous dispersions of graphene, it is stirred to react at 55 DEG C 5 hours, reaction product is put into after ethyl alcohol washs in vacuum drying oven,
It is dry to constant weight at 55 DEG C, it is promoted the graphene of agent modification（M-G）.Characteristic in order to better illustrate the present invention, is pressed
Existing conventional method is prepared for the graphene of hydrazine hydrate reduction, is named as H-G, to compare, similarly hereinafter.
The infrared spectrogram of M-G and GO manufactured in the present embodiment（FTIR）As shown in Figure 1.As seen from the figure, compare GO's
FTIR spectrograms, the spectrogram of M-G is in 1720 cm-1、1624 cm-1、 1376 cm-1、1054 cm-1The oxygen-containing functional group absorption peak at place
Apparent weaken even disappears, this explanation can effectively restore GO.In addition, there is C-N and C-S in the spectrogram of M-G（1100~
1400 cm-1Near）Characteristic peak, this illustrates captax by chemical covalent bonds used load on the surface of graphene.Promote
The reduction effect of GO can also be obtained from the result of the high-resolution x-ray photoelectron spectroscopy figure (XPS) in Fig. 2 a, Fig. 2 b into agent M
To confirmation.As can be observed from Figure, C=O bond, the peak intensity of carbon oxygen singly-bound are very high in GO, and after reduction, carbon oxygen
The peak intensity of functional group obviously weakens, and GO can effectively be restored by again demonstrating accelerating agent.The thermal weight loss that Fig. 3 is GO and M-G is bent
Line chart is shown in figure, the mass fraction in M-G contained by captax about 25%.Fig. 4 a are the transmission electron microscope photos of M-G, and Fig. 4 b are
The EDS element sulphur distribution maps of M-G.There are element sulphurs from Fig. 4 b as can be seen that on graphene, show passing through of accelerating agent
Effect is grafted on the graphene surface after reduction.
It is compound with M-G manufactured in the present embodiment and H-G and butadiene-styrene rubber (SBR), prepare SBR composite materials (SBR/M-G and
H-G), it is formulated as follows（Unit：phr）SBR 100；Captax；Zinc oxide 5；Stearic acid 2；Sulphur 1.6；Filler（M-G or
H-G）4.It should be pointed out that the M of M-G surface graftings needs to calculate in total accelerating agent number, to ensure all formula institutes
Number containing accelerating agent is identical.
Static mechanical property the results show that M-G is more preferable to the reinforcing effect of the reinforcing effect ratio H-G of SBR, tensile strength from
5.8MPa is increased to 13.8MPa, and thermal conductivity improves 32%.Dynamic Viscoelastic performance is the results show that SBR/M-G rubber composite materials
There is higher fissipation factor (Tan δ) at 0 DEG C than SBR/H-G rubber composite material（Improve 20%）, and possess at 60 DEG C compared with
Low Tan δ values（Reduce by 38%）.It these results suggest that, the wet-sliding resistant performance of SBR/M-G rubber composite materials improves, rolling resistance
Decline, illustrates that M-G has a good application prospect in rubber for tire composite material, can effectively reduce automobile fuel consumption and tail gas
Discharge meets the strategy of sustainable development of national " energy-saving and emission-reduction ".
Embodiment 2
200mg graphite oxides are distributed in 400ml deionized waters, ultrasound stripping forms graphene oxide（GO）It is water-dispersed
Liquid.By 100mg rubber accelerator diphenylguanidine（Diphenylguanidine）It is dissolved in 20ml toluene, and is added in above-mentioned GO aqueous dispersions,
It being stirred to react at 30 DEG C 2 hours, reaction product is put into after ethyl alcohol washs in vacuum drying oven, at 50 DEG C, drying to constant weight,
It is promoted the graphene that agent D is modified（D-G）.
FTIR and13The results show that compared with GO, the oxygen-containing functional group peak intensity in D-G is substantially reduced C nuclear-magnetisms, while
Occur organic peak on spectrogram, illustrate that diphenylguanidine can effectively restore GO, and after thering is part accelerating agent to be supported on and be reduced
Surface of graphene oxide.
It is compound with D-G manufactured in the present embodiment and H-G and butadiene-styrene rubber (SBR), prepare SBR composite materials (SBR/D-G and
H-G), for formula in addition to changing captax into M, remaining is same as Example 1, while ensureing the rush contained by all formulas
It is identical into agent number.The results show that D-G is evenly dispersed with monolithic layer in SBR matrixes.The stretching of SBR/D-G composite materials is strong
Degree and tearing strength ratio SBR/H-G composite materials are higher by 2.6MPa and 1.9kN/m respectively.
Embodiment 3
150mg graphite oxides are distributed in 100ml deionized waters, ultrasound stripping forms graphene oxide（GO）It is water-dispersed
Liquid.By 450mg rubber accelerators N, N '-diethyl thiourea（DETU）It is dissolved in 30ml toluene, and it is water-dispersed to be added to above-mentioned GO
It in liquid, is stirred to react at 80 DEG C 8 hours, reaction product is put into after ethyl alcohol washs in vacuum drying oven, dry at 60 DEG C
To constant weight, it is promoted the graphene that agent DETU is modified（DETU-G）.
FTIR and XPS nuclear-magnetisms are the results show that compared with GO, and the oxygen-containing functional group peak intensity in DETU-G is substantially reduced, together
When occur organic peak on spectrogram, illustrate that diphenylguanidine ETU can effectively restore GO, and have part accelerating agent pass through chemistry make
With being supported on the surface of graphene oxide after being reduced.
It is compound with DETU-G manufactured in the present embodiment and H-G and butadiene-styrene rubber (SBR), prepare SBR composite materials (SBR/
DETU-G and H-G), it is formulated in addition to changing captax into DETU, remaining is same as Example 1, while ensureing all formulas
Contained accelerating agent number is identical.The results show that DETU-G is evenly dispersed with monolithic layer in SBR matrixes.SBR/DETU-G
Tensile strength and tearing strength the ratio SBR/H-G composite materials of composite material are higher by 2.9MPa and 2.1kN/m respectively.SBR/ simultaneously
The Tc10 ratio SBR/H-G composite materials of DETU-G composite materials improve 38 seconds, and Tc90 ratio SBR/H-G composite materials reduce by 170
Second.
Embodiment 4
100mg graphite oxides are distributed in 100ml deionized waters, ultrasound stripping forms graphene oxide（GO）It is water-dispersed
Liquid.By 100mg rubber accelerator ethylene thioureas（ETU）It is dissolved in 17ml absolute ethyl alcohols, and is added to above-mentioned GO aqueous dispersions
In, it is stirred to react at 35 DEG C 6 hours, reaction product is put into after ethyl alcohol washs in vacuum drying oven, and at 35 DEG C, drying is extremely
Constant weight is promoted the graphene that agent ETU is modified（ETU-G）.
XPS and nuclear magnetic resonance13C is the results show that accelerating agent ETU can effectively restore GO, and have accelerating agent to be supported on quilt
Surface of graphene oxide after reduction.
It is compound with ETU-G manufactured in the present embodiment and H-G and natural rubber (NR), prepare NR composite materials (NR/ETU-G
And H-G), it is formulated in addition to changing captax into ETU, remaining is same as Example 1, while ensureing contained by all formulas
Accelerating agent number it is identical.The results show that ETU-G is evenly dispersed and can significantly improve day with monolithic layer in natural rubber matrix
The curability of T PNR.The tensile strength ratio NR/H-G composite materials of NR/ETU-G composite materials are higher by 2.8MPa respectively.
Embodiment 5
100mg graphite oxides are distributed in 100ml deionized waters, ultrasound stripping forms graphene oxide（GO）It is water-dispersed
Liquid.By two o-methyl-benzene guanidine of 100mg rubber accelerators（DOTG）It is dissolved in 17ml absolute ethyl alcohols, and it is water-dispersed to be added to above-mentioned GO
It in liquid, is stirred to react at 35 DEG C 6 hours, reaction product is put into after ethyl alcohol washs in vacuum drying oven, dry at 35 DEG C
To constant weight, it is promoted the graphene that agent DOTG is modified（DOTG-G）.
XPS and nuclear magnetic resonance13C is the results show that diphenylguanidine OTG can effectively restore GO, and have accelerating agent to be supported on quilt
Surface of graphene oxide after reduction.
It is compound with DOTG-G manufactured in the present embodiment and H-G and natural rubber (NR), prepare NR composite materials (NR/DOTG-
G and H-G), it is formulated in addition to changing captax into DOTG, remaining is same as Example 1, while ensureing contained by all formulas
Some accelerating agent numbers are identical.The results show that DOTG-G is evenly dispersed and can significantly carry with monolithic layer in natural rubber matrix
The curability of high natural rubber.NR/DOTG-G composite materials have higher fissipation factor at 0 DEG C（Tanδ）（It improves
10%）, and possess lower Tan δ at 60 DEG C（Reduce by 8%）.
Claims (10)
1. a kind of preparation method of thiofide reduction and modified graphene oxide, which is characterized in that including following step
Suddenly：
(1) graphite oxide is added to the water, ultrasound stripping obtains the aqueous dispersions of graphene oxide；
(2) rubber accelerator is dissolved in organic solvent or water, forms rubber accelerator solution；
(3) the rubber accelerator solution is mixed with the aqueous dispersions of graphene oxide, is stirred to react at 30~80 DEG C；
(4) by reaction product washing obtained by step (3), be dried in vacuo to get to thiofide reduction and modified oxidized
Graphene.
2. preparation method according to claim 1, which is characterized in that the aqueous dispersions of step (1) described graphene oxide
A concentration of 0.5~1.5mg/ml.
3. preparation method according to claim 1, which is characterized in that step (2) described rubber accelerator is 2- sulfydryl benzene
And thiazole, zinc 2-mercaptobenzothiazole salt, ethylene thiourea, N, in N '-diethyl thioureas, diphenylguanidine and two o-methyl-benzene guanidines
One kind.
4. preparation method according to claim 1, which is characterized in that step (2) described organic solvent be methanol, ethyl alcohol,
One or more of toluene, benzene, dimethylbenzene, acetone, ether and chloroform mixed solvent.
5. preparation method according to claim 1, which is characterized in that the quality of step (2) described rubber accelerator is oxygen
0.5~3 times of graphite quality.
6. preparation method according to claim 1, which is characterized in that the concentration of step (2) the rubber accelerator solution
For 5~15mg/ml.
7. preparation method according to claim 1, which is characterized in that step (3) time being stirred to react is 2~8
Hour.
8. preparation method according to claim 7, which is characterized in that the time being stirred to react is 3-7 hours.
9. a kind of thiofide reduction made from claim 1-8 any one of them preparation methods and modified oxidized
Graphene.
10. a kind of reduction of thiofide and modified graphene oxide described in claim 9 are applied to rubber composite wood
In material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942908A (en) * | 2019-03-05 | 2019-06-28 | 华南理工大学 | A kind of application of modified graphene in blend rubber |
| CN111440442A (en) * | 2020-04-30 | 2020-07-24 | 安徽大学 | Polysulfide oligomer modified graphene oxide for modified polysulfide sealant and modification method 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 |
| CN112876751A (en) * | 2021-03-29 | 2021-06-01 | 青岛科技大学 | Janus-like graphene/natural latex composite membrane and preparation method thereof |
| CN114591636A (en) * | 2022-01-22 | 2022-06-07 | 中北大学 | Vulcanizing agent modified graphene prepared by chemical in-situ deposition process and controllable cross-linked natural rubber composite material thereof |
| CN114874499A (en) * | 2021-02-05 | 2022-08-09 | 北京化工大学 | Graphene oxide loaded rare earth vulcanization accelerator and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224656A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Oxidized grapheme/carbon black rubber nanocomposite and preparation method thereof |
| CN105801943A (en) * | 2016-05-31 | 2016-07-27 | 青岛双星轮胎工业有限公司 | Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound |
| CN106589460A (en) * | 2016-12-13 | 2017-04-26 | 华南理工大学 | Rubber chemical reduced and modified graphene oxide as well as preparation method and application thereof |
| 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 |
-
2018
- 2018-03-14 CN CN201810207294.3A patent/CN108314014A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224656A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Oxidized grapheme/carbon black rubber nanocomposite and preparation method thereof |
| CN105801943A (en) * | 2016-05-31 | 2016-07-27 | 青岛双星轮胎工业有限公司 | Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound |
| CN106589460A (en) * | 2016-12-13 | 2017-04-26 | 华南理工大学 | Rubber chemical reduced and modified graphene oxide as well as preparation method and application thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| ZHENG-TIAN XIE，ET AL.: ""New evidence disclosed for the engineered strong interfacial interaction of graphene/rubber nanocomposites"", 《POLYMER》 * |
| 唐征海 等: ""石墨烯/橡胶纳米复合材料"", 《高分子学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942908A (en) * | 2019-03-05 | 2019-06-28 | 华南理工大学 | A kind of application of modified graphene in blend rubber |
| CN111440442A (en) * | 2020-04-30 | 2020-07-24 | 安徽大学 | Polysulfide oligomer modified graphene oxide for modified polysulfide sealant and modification method 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 |
| CN114874499A (en) * | 2021-02-05 | 2022-08-09 | 北京化工大学 | Graphene oxide loaded rare earth vulcanization accelerator and preparation method thereof |
| CN112876751A (en) * | 2021-03-29 | 2021-06-01 | 青岛科技大学 | Janus-like graphene/natural latex composite membrane and preparation method thereof |
| CN114591636A (en) * | 2022-01-22 | 2022-06-07 | 中北大学 | Vulcanizing agent modified graphene prepared by chemical in-situ deposition process and controllable cross-linked natural rubber composite material thereof |
| CN114591636B (en) * | 2022-01-22 | 2023-09-22 | 中北大学 | Vulcanizing agent modified graphene prepared by chemical in-situ deposition process and controllable crosslinked natural rubber composite material thereof |
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