阅读说明：本技术 一种利用静电纺丝工艺制备氧化石墨烯eva橡胶的方法 (Method for preparing graphene oxide EVA rubber by utilizing electrostatic spinning process ) 是由 张弦 易汉平 孙丽娅 吴珍 周杰 刘乐 张婷 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种利用静电纺丝工艺制备氧化石墨烯EVA橡胶材料的方法,包括如下制备过程：S1.超声分散；S2.混合；S3.静电纺丝；S4.制得氧化石墨烯EVA橡胶材料。本发明利用了氧化石墨烯不易团聚的特点,且通过超声分散,可将氧化石墨烯粉均匀分散于溶剂中,制得的氧化石墨烯EVA橡胶,氧化石墨烯均匀分散于EVA橡胶中,二维结构的氧化石墨烯与EVA橡胶进行交联,强化了其强度。而且,本发明利用静电纺丝工艺制备氧化石墨烯EVA橡胶,进一步对氧化石墨烯与EVA橡胶进行分散和结构键合,进一步强化了其强度,与不加石墨烯的EVA橡胶相比密度较小、力学性能更好的特点。(The invention discloses a method for preparing a graphene oxide EVA rubber material by utilizing an electrostatic spinning process, which comprises the following preparation processes: s1, ultrasonic dispersion; s2, mixing; s3, electrostatic spinning; and S4, preparing the graphene oxide EVA rubber material. According to the invention, the characteristic that graphene oxide is not easy to agglomerate is utilized, and graphene oxide powder can be uniformly dispersed in a solvent through ultrasonic dispersion, so that the prepared graphene oxide EVA rubber has the advantages that graphene oxide is uniformly dispersed in the EVA rubber, and the graphene oxide with a two-dimensional structure is crosslinked with the EVA rubber, so that the strength of the graphene oxide EVA rubber is enhanced. In addition, the graphene oxide EVA rubber is prepared by using an electrostatic spinning process, and the graphene oxide and the EVA rubber are further dispersed and structurally bonded, so that the strength of the graphene oxide EVA rubber is further enhanced, and the graphene oxide EVA rubber has the characteristics of smaller density and better mechanical property compared with the EVA rubber without the graphene.)

1. A method for preparing a graphene oxide EVA rubber material by utilizing an electrostatic spinning process is characterized by comprising the following preparation processes: s1, ultrasonic dispersion; s2, mixing; s3, electrostatic spinning; s4, preparing a graphene oxide EVA rubber material, specifically:

s1, ultrasonic dispersion: dissolving graphene oxide powder in a solvent to prepare a solution of 0.2-0.5mg/mL, adding a dispersing agent for ultrasonic dispersion, wherein the concentration of the dispersing agent is 0.02-0.05mg/mL, the ultrasonic power is 500-2000W, the frequency is 10-50KHz, and the ultrasonic time is 30-90min to obtain a graphene oxide solution;

s2, mixing: adding 5-10% (w/v) of EVA rubber raw material into the graphene oxide solution prepared in the S1. ultrasonic dispersion, stirring and dispersing at the stirring speed of 1000-5000rpm for 30-120min to obtain a mixture of graphene oxide and EVA rubber;

s3, electrostatic spinning: s2, sucking the mixed material obtained in the mixing by using an injector, and spinning on electrostatic spinning equipment, wherein the voltage of an electric field is 5-10KV, and the distance between the needle of the injector and a collecting plate is kept at 10-20cm to obtain a graphene oxide reinforced EVA rubber material;

s4, preparing a graphene oxide EVA rubber material: s3, mixing the graphene oxide reinforced EVA rubber material obtained by electrostatic spinning with the rubber raw material and the filler according to the proportion of 1: (5-10): (1-5), after open milling for 5-10min at 90-110 ℃, adding 0.01-0.05 part of anti-aging agent, 0.02-0.08 part of wear-resisting agent, 0.002-0.010 part of accelerator, 0.02-0.05 part of vulcanizing agent, 0.01-0.05 part of dispersing agent and 0.01-0.02 part of reducing agent into each part of the mixture, banburying at 50-100 ℃ for 2-5min, and finally vulcanizing at 150-.

2. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the solvent is one or two of water, methanol, ethanol, acetone and acetonitrile.

3. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the dispersing agent is one of N-methyl-2-pyrrolidone, sodium dodecyl benzene sulfonate and p-dimethyl benzene dicarboxylic acid.

4. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the rubber raw material is one or a combination of any two of natural rubber, EVA rubber, polybutadiene, butadiene rubber, styrene-butadiene rubber and nitrile-butadiene rubber.

5. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the filler is any one of white carbon black, carbon fiber, carbon nanotube and porous carbon.

6. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the anti-aging agent is any one of benzoquinone, 2-hydroxybenzophenone and 2-benzotriazole.

7. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the anti-abrasion agent is any one of zinc oxide, zinc carbonate, magnesium oxide and magnesium carbonate.

8. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the accelerator is any one of 3-methylthiazolidine-thione-2, N-tert-butyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-tetramethyldithiobisthiocarboxamine, and N- (oxydiethylene) -2-benzothiazolesulfenamide.

9. The method for preparing the graphene oxide EVA rubber material by using the electrostatic spinning process according to claim 1, wherein the vulcanizing agent is any one of sulfur, hydrogen sulfide and sodium sulfide.

10. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the dispersant is any one of stearic acid, oleic acid and paraffin.

11. The method for preparing the graphene oxide EVA rubber material by using the electrospinning process according to claim 1, wherein the reducing agent is any one of hydrazine hydrate, hydroxylamine hydrochloride and thiourea.

The technical field is as follows:

the invention relates to a method for preparing graphene oxide EVA rubber, in particular to a method for preparing a graphene oxide EVA rubber material by utilizing an electrostatic spinning process.

Background art:

graphene is a carbon material with a thickness of a single atomic layer formed by connecting carbon atoms with each other in a sp2 hybridization mode on a two-dimensional plane, wherein the carbon atoms are arranged in a hexagonal honeycomb shape and are the only two-dimensional free state atom crystal which exists at present. The arrangement form enables the graphene to have the characteristics of lightness, thinness, high strength, high hardness, strong deformability and the like, and when the graphene rubber composite material is added into a rubber material to prepare the graphene rubber composite material, the performance of the rubber material can be improved to a certain extent; however, according to the existing published data, when the graphene rubber composite material is used as a substrate of leather shoes, sports shoes and rubber shoes, the graphene has the characteristics of hydrophobicity and easy agglomeration due to strong van der waals force, so that the graphene is not easy to disperse when the graphene rubber composite material is prepared, and thus the performance of the rubber material can be improved to a certain extent by the graphene rubber composite material, but the expectation of consumers on high-grade leather shoes, sports shoes and rubber shoes can not be met, so that the preparation of the leather shoes, sports shoes and rubber shoes by the graphene rubber material is greatly limited.

The invention content is as follows:

the invention aims to overcome the defects of the prior art and provides a method for preparing a graphene oxide EVA rubber material by using an electrostatic spinning process.

The invention is implemented by the following technical scheme: a method for preparing a graphene oxide EVA rubber material by utilizing an electrostatic spinning process comprises the following preparation processes:

s1, ultrasonic dispersion: dissolving graphene oxide powder in a solvent to prepare a solution of 0.2-0.5mg/mL, adding a dispersing agent to perform ultrasonic dispersion, wherein the concentration of the dispersing agent is 0.02-0.05mg/mL, and performing ultrasonic dispersion, wherein the ultrasonic power is 500-2000W, the frequency is 10-50KHz, and the ultrasonic time is 30-90min to obtain a graphene oxide solution;

s2, mixing: adding 5-10% (w/v) of EVA rubber raw material into the graphene oxide solution prepared in the S1. ultrasonic dispersion, stirring and dispersing at the stirring speed of 1000-5000rpm for 30-120min to obtain a mixture of graphene oxide and EVA rubber;

s3, electrostatic spinning: s2, sucking the mixed material obtained in the mixing by using an injector, and spinning on electrostatic spinning equipment, wherein the voltage of an electric field is 5-10KV, and the distance between the needle of the injector and a collecting plate is kept at 10-20cm to obtain a graphene oxide reinforced EVA rubber material;

s4, preparing a graphene oxide EVA rubber material: s3, mixing the graphene oxide reinforced EVA rubber material obtained by electrostatic spinning with the rubber raw material and the filler according to the proportion of 1: (5-10): (1-5), after open milling for 5-10min at 90-110 ℃, adding 0.01-0.05 part of anti-aging agent, 0.02-0.08 part of wear-resistant agent, 0.002-0.010 part of accelerator, 0.02-0.05 part of vulcanizing agent, 0.01-0.05 part of dispersing agent and 0.01-0.02 part of reducing agent, banburying at 50-100 ℃ for 2-5min, and finally vulcanizing at 150-200 ℃ for 2-5min to obtain the graphene oxide EVA rubber material.

Further, the solvent is one or two of water, methanol, ethanol, acetone and acetonitrile;

further, the rubber raw material is one or a combination of any two of natural rubber, EVA rubber, polybutadiene, butadiene rubber, styrene butadiene rubber and nitrile butadiene rubber.

Further, the filler is any one of white carbon black, carbon fiber, carbon nanotube and porous carbon.

Further, the anti-aging agent is any one of benzoquinone, 2-hydroxybenzophenone and 2-benzotriazole.

Further, the anti-abrasion agent is any one of zinc oxide, zinc carbonate, magnesium oxide and magnesium carbonate.

Further, the accelerator is any one of 3-methylthiazolidine-thione-2, N-tert-butyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N' -tetramethyldithiodithiobisthiocarboxamine and N- (oxydiethylene) -2-benzothiazolesulfenamide.

Further, the vulcanizing agent is any one of sulfur, hydrogen sulfide and sodium sulfide.

Further, the dispersant is any one of stearic acid, oleic acid and paraffin.

Further, the reducing agent is any one of hydrazine hydrate, hydroxylamine hydrochloride and thiourea.

The invention has the advantages that: according to the invention, by utilizing the characteristic that graphene oxide is not easy to agglomerate, and then carrying out electrostatic spinning process operation on the graphene oxide and the EVA rubber raw material, the dispersed graphene oxide and the EVA rubber can be prepared into a nano-filament structure, and the graphene oxide and the EVA rubber are subjected to dispersion and structural bonding, so that the strength and tensile property of the material are improved. In addition, after subsequent mixing and crosslinking, the two-dimensional filamentous material can form a stable three-dimensional microstructure, which is beneficial to further reducing the density of the material and improving the performance of the material.

The specific implementation mode is as follows:

the method for preparing the graphene oxide EVA rubber material of the present invention is further described in detail by the following specific examples, wherein in the present embodiment, the parts are all parts by weight, and the ratio is a mass ratio.