阅读说明：本技术 一种石墨烯耐磨橡塑发泡鞋材及制备方法 (Graphene wear-resistant rubber-plastic foamed shoe material and preparation method thereof ) 是由 陈庆 昝航 曾军堂 于 2019-11-18 设计创作，主要内容包括：本发明涉及橡塑发泡材料领域,具体涉及耐磨的橡塑发泡鞋材料及制备方法,所述制备方法包括如下步骤：将石墨烯与铝粉按照质量比5:1混合,在660~680℃高温熔炼混合均匀后,再经喷雾法得到片状纳米级的石墨烯/铝粉末；将聚碳酸酯二醇和4,4’-二苯基甲烷二异氰酸酯、辛酸亚锡混合均匀,再加入石墨烯/铝粉末和六偏磷酸钠,在80~100℃搅拌反应得到聚氨酯弹性体；将聚氨酯弹性体与EVA、NR橡胶、无机填料、润滑剂、硫磺、AC发泡剂、防老剂在密炼机90~100℃混炼4~6min,然后出片；将片裁切,植入模压170~200℃发泡180~240s得到一种石墨烯耐磨橡塑发泡鞋材。本发明的鞋材的低温耐磨性好。(The invention relates to the field of rubber and plastic foam materials, in particular to a wear-resistant rubber and plastic foam shoe material and a preparation method thereof, wherein the preparation method comprises the following steps of mixing graphene and aluminum powder according to a mass ratio of 5:1, smelting and mixing the mixture uniformly at a high temperature of 660 ~ 680 ℃, then obtaining flaky nanoscale graphene/aluminum powder through a spraying method, mixing polycarbonate diol, 4' -diphenylmethane diisocyanate and stannous octoate uniformly, adding graphene/aluminum powder and sodium hexametaphosphate, stirring and reacting at a temperature of 80 ~ 100 ℃ to obtain a polyurethane elastomer, mixing the polyurethane elastomer with EVA, NR rubber, an inorganic filler, a lubricant, sulfur, an AC foaming agent and an anti-aging agent for 4 ~ 6min at a temperature of 90 ~ 100 ℃ of an internal mixer, then discharging the mixture, cutting the sheet, and implanting the rubber and plastic into a mold for molding at a temperature of 170 ~ 200 ℃ for 180 ~ 240s to obtain the graphene wear-resistant foam shoe material.)

1. A preparation method of a graphene wear-resistant rubber and plastic foamed shoe material is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing graphene and aluminum powder according to a mass ratio of 5:1 to obtain mixed powder, smelting and uniformly mixing the mixed powder at a high temperature of 660 ~ 680 ℃, and then obtaining flaky nanoscale graphene/aluminum powder by a spraying method;

(2) uniformly mixing polycarbonate diol, 4' -diphenylmethane diisocyanate and stannous octoate, adding the flaky nanoscale graphene/aluminum powder prepared in the step (1) and a sodium hexametaphosphate dispersant, and stirring at 80 ~ 100 ℃ to react to obtain a polycarbonate type polyurethane elastomer containing graphene/aluminum;

(3) mixing the polycarbonate type polyurethane elastomer containing graphene/aluminum obtained in the step (2) with EVA, NR rubber, inorganic filler, lubricant, sulfur, AC foaming agent and anti-aging agent according to the mass ratio of 8:50 ~ 100:5 ~ 10:3 ~ 5:1 ~ 2:1.5 ~ 3:0.05 ~ 0.2.2: 0.5 ~ 1 in an internal mixer, adjusting the internal mixing temperature to 90: 90 ~ 100 ℃, mixing for 4 ~ 6min, and then discharging the sheets by an open mill;

(4) and (4) cutting the sheet obtained in the step (3) according to requirements, implanting the sheet into a mould for mould pressing and foaming, controlling the foaming temperature to be 170 ~ 200 ℃ and the foaming time to be 180 ~ 240s, and obtaining the graphene wear-resistant rubber and plastic foamed shoe material.

2. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1, characterized by comprising the following steps: and (2) carrying out high-temperature smelting under the protection of inert gas in the step (1).

3. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, characterized by comprising the following steps: the size of the flaky nanoscale graphene/aluminum powder in the step (1) is less than 100 nm.

4. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, wherein the mixed powder in the step (1) is melted and mixed uniformly at a high temperature of 660 ~ 665 ℃.

5. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, wherein the mass ratio of the polycarbonate diol in the step (2) to the 4, 4' -diphenylmethane diisocyanate, the stannous octoate, the flaky nanoscale graphene/aluminum powder and the sodium hexametaphosphate dispersant is 100:50 ~ 90:0.4 ~ 1.2.2: 5 ~ 16:1 ~ 5.

6. The method for preparing the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, wherein the polycarbonate type polyurethane elastomer containing graphene/aluminum in the step (3) is mixed with EVA, NR rubber, an inorganic filler, a lubricant, sulfur, an AC foaming agent and an anti-aging agent in a mass ratio of 8:60 ~ 80:5 ~ 8:3 ~ 5: 5 1 ~ 2:1.5 ~ 2:0.05 ~ 0.2.2: 0.6 ~ 0.8.8.

7. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, wherein the banburying temperature in the step (3) is controlled at 95 ~ 100 ℃ and is mixed for 4 ~ 5 min.

8. The preparation method of the graphene wear-resistant rubber-plastic foamed shoe material according to claim 1 or 2, wherein the foaming temperature in the step (4) is 180 ~ 190 ℃ and the foaming time is 180 ~ 200 s.

9. The graphene wear-resistant rubber-plastic foamed shoe material is prepared according to the method of any one of claims 1 ~ 6.

Technical Field

The invention relates to the field of rubber and plastic foam materials, in particular to a wear-resistant rubber and plastic foam shoe material and a preparation method thereof, and particularly relates to a low-temperature wear-resistant ethylene-vinyl acetate copolymer foam shoe material and a preparation method thereof.

Background

The foaming material is obtained by adding auxiliary materials such as a catalyst, a foam stabilizer, a foaming agent and the like into raw materials such as plastics and the like, and enabling a large amount of fine foams to appear in the raw materials such as the plastics and the like through physical foaming or cross-linking foaming. The volume of the foamed material is increased and the density is reduced after the foaming of the raw materials such as plastic and the like, and the obtained foamed material has the functions of buffering, shock absorption, heat preservation and the like. Ethylene-vinyl acetate copolymer (EVA) foam materials have excellent flexibility, elasticity, and chemical resistance, and are gradually accepted by shoe sole manufacturers. In particular, the EVA foaming sole material has attracted more and more attention when being compounded with high-elasticity rubber to prepare high-elasticity foaming materials, and gradually replaces polyurethane sole materials to become the mainstream of sports shoe materials.

The EVA foaming material has the characteristics of slipping, puncture resistance, low-temperature hardening and the like. The elastomer and EVA have good compatibility, a disperse phase is easily formed in a system, the acting force between molecular chains can be reduced, the plasticizing effect is achieved, the addition of the elastomer material can improve the compression deformation, wear resistance, skid resistance, folding resistance and other properties of the EVA foaming material, and the material with low price and more excellent performance is prepared to meet the special requirements of people on the material performance. Meanwhile, the density and the tearing strength of the EVA foaming material are basically unchanged, the tensile strength and the hardness are in a descending trend, the elongation at break is increased, and the flexibility of the material is improved.

In recent years, composite foaming materials of EVA and various chloroprene rubbers, natural rubber, butyl rubber and the like have excellent elasticity at normal temperature, but the elasticity and the tensile property of the composite foaming material elastomer are seriously deteriorated at low temperature, mainly appear to be hardened and brittle fracture at low temperature, are difficult to meet the actual use requirement, have unsatisfactory wear resistance, and limit the large-scale application of the EVA foaming material in shoe materials.

Chinese patent application No. 2018101090200 discloses a wear-resistant EVA-based composite material and a preparation method thereof, wherein 20 parts by mass of SBS, 30 parts by mass of SBR, 50 parts by mass of EVA, 40 parts by mass of dynamic vulcanization predispersion glue, 5-7 parts by mass of antioxidant, 3-4 parts by mass of ZnO, 0.5-1 part by mass of Hst, 2-3 parts by mass of accelerator, 0.5-1 part by mass of S, 1-2 parts by mass of DCP and 3-5 parts by mass of foaming agent are adopted. The wear-resistant EVA-based composite material prepared by the invention has the advantages of excellent wear resistance, high elasticity, good resilience, stable size and good mechanical property, and can be used for soles of sports shoes.

The Chinese patent application No. 2018116011790 discloses a low-temperature-resistant wear-resistant TPU composite material for mountain climbing boots and a preparation method thereof, belonging to the technical field of polyurethane. The TPU composite material comprises the following raw materials in percentage by weight: 80-92% of TPU master batch, 5-13% of ABS resin, 0.1-0.5% of modified carbon nanofiber, 0.1-0.5% of hydrolysis resistance agent, 0.1-0.5% of antioxidant, 1-5% of polyvinyl fluoride and 0.2-0.5% of polyethylene wax; the TPU master batch is prepared by taking oligomeric polyol, diisocyanate, a chain extender and nano SiO2 as raw materials through a double-screw extruder. The TPU composite material disclosed by the invention not only has excellent wear resistance and low temperature resistance, but also has good mechanical property and rebound resilience, and is excellent in stability in the production process, so that the TPU composite material can be widely applied to the field of shoe materials; the invention also provides a simple and feasible preparation method.

The Chinese patent application No. 2019100688052 discloses a low-temperature cold-resistant material, which comprises the following raw material components in parts by weight: thermoplastic plastics: 35-45 parts of a solvent; 45-55 parts of isoprene liquid rubber; 2-4 parts of a silane coupling agent; 4-8 parts of calcium powder; 0.5-1.5 parts of stearic acid. The invention also discloses a low-temperature cold-resistant sole comprising the low-temperature cold-resistant material and a preparation process thereof. The invention has the advantages that: the sole has good comprehensive performance and low cost, particularly has good low-temperature cold resistance and folding resistance, and is suitable for manufacturing sports shoes.

Chinese invention patent application no: 2019103808215 discloses a graphene rubber-plastic foamed insole and a preparation method thereof, which is prepared from the following raw materials in parts by weight: 48-54 parts of ethylene-vinyl acetate copolymer, 12-16 parts of methyl vinyl silicone rubber, 20-24 parts of styrene-butadiene-styrene block copolymer, 10-15 parts of thermoplastic polyester elastomer, 8-12 parts of polyester-polyether block copolymer, 6-9 parts of EVA color master, 5-9 parts of PE color master, 2.5-4.4 parts of aluminum silicate fiber tube, 7-10 parts of graphene, 3-5 parts of plasticizer, 0.8-1.2 parts of bridging agent, 1.4-2.5 parts of foaming agent, 0.8-1.2 parts of micropore regulator, 2.5-4 parts of antioxidant, 1-1.7 parts of crosslinking agent and 3-6 parts of zinc stearate. The graphene rubber-plastic foamed insole is high in rebound rate and excellent in mechanical property; the moisture absorption performance is good, the air permeability is good, and the wearing is comfortable; after the water-based polyurethane foam is used for a period of time, the elasticity is still kept good, and the water absorption and air permeability are also kept good. In addition, the hardness is moderate, and the pillow is more comfortable and more textured.

Disclosure of Invention

Aiming at the problems that the EVA-based shoe material is easy to harden at low temperature and has poor wear resistance, the invention provides a preparation method of a graphene wear-resistant rubber-plastic foamed shoe material.

In order to solve the problems, the invention adopts the following technical scheme:

a preparation method of a graphene wear-resistant rubber and plastic foamed shoe material comprises the following steps:

(1) mixing graphene and aluminum powder according to a mass ratio of 5:1 to obtain mixed powder, smelting and uniformly mixing the mixed powder at a high temperature of 660 ~ 680 ℃, and then obtaining flaky nanoscale graphene/aluminum powder by a spraying method;

(2) uniformly mixing polycarbonate diol, 4' -diphenylmethane diisocyanate and stannous octoate, adding the flaky nanoscale graphene/aluminum powder prepared in the step (1) and a sodium hexametaphosphate dispersant, and stirring at 80 ~ 100 ℃ to react to obtain a polycarbonate type polyurethane elastomer containing graphene/aluminum;

(3) mixing the polycarbonate type polyurethane elastomer containing graphene/aluminum obtained in the step (2) with EVA, NR rubber, inorganic filler, lubricant, sulfur, AC foaming agent and anti-aging agent according to the mass ratio of 8:50 ~ 100:5 ~ 10:3 ~ 5:1 ~ 2:1.5 ~ 3:0.05 ~ 0.2.2: 0.5 ~ 1 in an internal mixer, adjusting the internal mixing temperature to 90: 90 ~ 100 ℃, mixing for 4 ~ 6min, and then discharging the sheets by an open mill;

(4) and (4) cutting the sheet obtained in the step (3) according to requirements, implanting the sheet into a mould for mould pressing and foaming, controlling the foaming temperature to be 170 ~ 200 ℃ and the foaming time to be 180 ~ 240s, and obtaining the graphene wear-resistant rubber and plastic foamed shoe material.

The graphene and the aluminum powder in the step (1) of the invention need to be uniformly mixed, and the mixing temperature is high, so that the mixing can be performed under the protection of an inert atmosphere, such as argon, but the cost of argon is slightly high, the cost of nitrogen is low, nitrogen easily reacts with aluminum at a high temperature, nitrogen can be used at a temperature lower than the reaction temperature of aluminum nitride, and nitrogen cannot be used at a temperature higher than the generation temperature of aluminum nitride.

The spraying method in step (1) of the present invention may employ a conventional spraying machine, the size of the sprayed product may be controlled by controlling the flow rate, pressure and nozzle size of the spray, and if the size of the obtained product is not uniform, the obtained product may be screened, for example, by screening graphene/aluminum powder in the form of nano-scale flakes of 100nm or less.

The flaky nanoscale graphene/aluminum powder obtained in the step (1) is mainly prepared by loading an aluminum simple substance on the surface of flaky graphene.

The NR rubber in step (3) of the present invention is a natural rubber.

The inorganic filler in step (3) of the present invention may be a conventional inorganic filler for polyurethane foaming, such as ground powder of natural inorganic mineral, e.g. calcium carbonate, barium sulfate, etc., and the particle size of the inorganic filler is 300 ~ 1500 mesh.

The lubricant in step (3) of the present invention is a lubricant commonly used for polyurethane foaming, such as stearic acid and its salts, paraffin wax, and stearamides.

The antioxidant in step (3) of the invention is a common antioxidant for rubber, such as nontoxic, tasteless and light antioxidant 4.4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, N-phenyl-2-naphthylamine and 2-mercaptobenzimidazole, and can also be mixed for use.

Preferably, the high-temperature smelting in the step (1) is carried out under the protection of inert gas.

Preferably, the size of the flaky nanoscale graphene/aluminum powder in step (1) is 100nm or less.

The temperature for high-temperature smelting of the mixed powder in the step (1) is not suitable to be too high, firstly, energy is wasted, secondly, burden is increased for next-step spraying, and the mixed powder is too low and can not be prepared into flaky nanoscale graphene/aluminum powder.

Preferably, the mass ratio of the polycarbonate diol and the 4, 4' -diphenylmethane diisocyanate, the stannous octoate, the flaky nanoscale graphene/aluminum powder and the sodium hexametaphosphate dispersant in the step (2) is 100:50 ~ 90:0.4 ~ 1.2.2: 5 ~ 16:1 ~ 5.

Experiments show that the comprehensive performance of the shoe material obtained by adding the graphene/aluminum polycarbonate type polyurethane elastomer and EVA, NR rubber, an inorganic filler, a lubricant, sulfur, an AC foaming agent and an anti-aging agent in a mass ratio of 8:60 ~ 80:5 ~: 3 ~: 1 ~ 12:1.5 ~: 0.05 ~.2: 0.6 ~.8 is good, so that the preferable results are that the graphene/aluminum-containing polycarbonate type polyurethane elastomer obtained in the step (3) and EVA, NR rubber, an inorganic filler, a lubricant, sulfur, an AC foaming agent and an anti-aging agent in a mass ratio of 8:60 ~: 5 ~: 3 ~: 1 ~: 1.5 ~ 2:0.05 ~.2: 0.6: ~.8.

Preferably, the banburying temperature in the step (3) is controlled to be 95 ~ 100 ℃ and is controlled to be 4 ~ 5min in mixing.

Preferably, the foaming temperature in the step (4) is 180 ~ 190 ℃ and the foaming time is 180 ~ 200 s.

The second purpose to be achieved by the invention is to provide the graphene wear-resistant rubber-plastic foamed shoe material, which is prepared by adopting the method.

Compared with the prior art, the invention has the outstanding characteristics and excellent effects that:

according to the preparation method of the graphene wear-resistant rubber-plastic foamed shoe material, the aluminum simple substance is loaded on the surface of the flaky graphene, and then the graphene simple substance is dispersed in the polycarbonate polyurethane elastomer, the modified elastomer is blended with EVA, and the graphene/aluminum synergistic effect is utilized, so that the low-temperature flexibility of the shoe material is enhanced, the shoe material has excellent wear resistance, and the purpose of prolonging the service life of the shoe material is achieved.

Drawings

FIG. 1: the shoe material prepared in example 1 was folded 1 ten thousand times to obtain a real figure without generating cracks and wrinkles.

FIG. 2 is a drawing: the shoe material prepared in comparative example 3 was folded 1 ten thousand times and showed severe cracking.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.