阅读说明：本技术 一种石墨烯添加物的天然橡胶抗静电鞋垫 (Natural rubber antistatic insole containing graphene additives ) 是由 丁天宁 丁德材 丁幼丝 于 2020-12-11 设计创作，主要内容包括：本发明提供一种石墨烯添加物的天然橡胶抗静电鞋垫,包括以下原料：天然橡胶,POE弹性体,三元乙丙胶,石墨烯,抗静电粉,氧化锌,硬脂酸锌,硬脂酸,无味交联剂,发泡剂。所述鞋垫材料制备流程如下：将用硬脂酸处理的石墨烯加热后,依次加入天然橡胶,POE弹性体,三元乙丙胶,在混炼机中进行混炼,得到混合原胶；再向混合原胶中加入抗静电粉,氧化锌,硬脂酸锌,无味交联剂,发泡剂进行再次混炼硫化交联,即得石墨烯抗静电鞋垫材料；然后将鞋垫材料根据需要裁减成相应的尺寸和厚度,该鞋垫具有抗静电、抗菌、弹性高、耐磨性好,无毒,不易变形,易清洁等优点。(The invention provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials: natural rubber, POE elastomer, ethylene propylene diene monomer, graphene, antistatic powder, zinc oxide, zinc stearate, stearic acid, an odorless crosslinking agent and a foaming agent. The preparation process of the insole material comprises the following steps: heating the graphene treated by stearic acid, sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll to obtain mixed virgin rubber; adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, and mixing, vulcanizing and cross-linking again to obtain the graphene antistatic insole material; then the insole material is cut into corresponding size and thickness according to the requirement, and the insole has the advantages of antistatic property, antibiosis, high elasticity, good wear resistance, no toxicity, difficult deformation, easy cleaning and the like.)

1. The natural rubber antistatic insole containing the graphene additive is characterized by comprising the following raw materials in parts by weight: 60-80 parts of natural rubber, 15-25 parts of POE (polyolefin elastomer), 5-15 parts of ethylene propylene diene monomer, 2-8 parts of graphene, 4-8 parts of antistatic powder, 4-8 parts of zinc oxide, 1-3 parts of zinc stearate, 1-3 parts of stearic acid, 0.5-2.0 parts of odorless cross-linking agent and 2-6 parts of foaming agent.

2. The natural rubber antistatic insole containing graphene additives according to claim 1, wherein the insole material comprises the following raw materials in parts by weight: 70 parts of natural rubber, 20 parts of POE (polyolefin elastomer), 10 parts of ethylene propylene diene monomer, 5 parts of graphene, 5 parts of antistatic powder, 6 parts of zinc oxide, 2 parts of zinc stearate, 2 parts of stearic acid, 1.0 part of odorless cross-linking agent and 4 parts of foaming agent.

3. The natural rubber antistatic insole containing graphene additives as claimed in claim 1 or 2, wherein the POE elastomer is one of ethylene-octene copolymer, ethylene-butene copolymer and ethylene-hexene copolymer.

4. The natural rubber antistatic insole containing graphene additives as claimed in claim 1 or 2, wherein the antistatic powder is one of ethoxylated aliphatic alkylamine, alkyl sodium sulfonate, alkyl imidazoline salt, polyethylene oxide, and polyether ester amide.

5. The natural rubber antistatic insole containing graphene additives according to claim 1 or 2, wherein the odorless cross-linking agent is di-tert-butylperoxydiisopropylbenzene; the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide.

6. A natural rubber antistatic insole containing the graphene additive according to claim 1 or 2, comprising the steps of:

step 1, heating the graphene treated by stearic acid, sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, and mixing, vulcanizing and cross-linking again to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

7. The natural rubber antistatic insole containing the graphene additive as claimed in claim 6, wherein the graphene treatment in step 1 specifically comprises the steps of mixing stearic acid and deionized water according to a weight ratio of 1-3: 100, uniformly mixing, heating to 100-160 ℃, slowly and gradually adding the graphene, continuously stirring during adding, continuously stirring for 1-3 hours after adding, and obtaining the stearic acid-treated graphene, wherein the adding amount of the graphene is 2-8 mg/ml.

8. The antistatic insole of natural rubber containing graphene additives as claimed in claim 6, wherein the mixing temperature in step 1 is 120-160 ℃ and the mixing time is 3-6 h.

9. The natural rubber antistatic insole containing the graphene additive as claimed in claim 6 is characterized in that during vulcanization crosslinking in step 2, the natural rubber antistatic insole containing the graphene additive is prepared by hot pressing on a flat vulcanizing machine at 120-160 ℃ and 8-10 MPa for 20-30 min, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h.

Technical Field

The invention belongs to the technical field of rubber-based composite materials, and particularly relates to a natural rubber antistatic insole containing graphene additives.

Background

The insole is widely applied to shoe making industry, health care and special functions; generally divided into two modes of application type shoe pad in shoe factory and market commodity. The insole applied in the shoe making industry is mainly matched with a shoe outsole and a shoe midsole to make a corresponding body; and manufacturing a size plate according to the last bottom plate or the last panel, and manufacturing a corresponding shape. The market commodity type insole is a product which is designed by developers and circulated in the market and is mainly sold as a commodity.

Insoles are classified according to their function and can be classified as health insoles, that is, insoles which are beneficial to human health, such as: antibacterial insoles, deodorant insoles, traditional Chinese medicine insoles and the like; the functional insole is a shoe insole with special functions, such as: antistatic insoles, heightening insoles, waterproof insoles, air circulation insoles and the like; a conventional insole is as follows: it is not the insole with the above 2 points, which is very common. The shoe pad is classified according to the material, and comprises an EVA shoe pad, a sponge shoe pad, a silica gel shoe pad, a TPR shoe pad, a latex shoe pad, a cloth shoe pad, a leather shoe pad, a CPU shoe pad and a cork shoe pad.

Common rubber insoles in the market at present are mainly soft rubber and hard rubber, and soft rubber is not worn well under the condition of humidity or sweating, but is worn quickly and is easy to deform; the hard rubber is durable, but has poor grip and comfort. Graphene is a polymer made of carbon atoms in sp²The two-dimensional carbon nano material with hexagonal honeycomb lattices formed by the hybrid tracks is used as a reinforcing material of rubber, the mechanical property of the rubber can be greatly improved by filling a small amount of the two-dimensional carbon nano material, and the two-dimensional carbon nano material can show good electrical and thermal properties and can be used as an ideal rubber addition material.

In order to solve the problems, the natural rubber antistatic insole with the graphene additive is developed, so that the elasticity is improved, and the toughness and the tearing resistance can be improved.

Disclosure of Invention

Based on the prior art, the invention aims to provide the natural rubber antistatic insole containing the graphene additive, which has the advantages of static resistance, bacteria resistance, deodorization, high elasticity, good wear resistance, strong toughness and tearing resistance, no toxicity, deformation resistance, easiness in cleaning and the like, can effectively improve the health condition of feet, and improves the comfort level and the appearance.

In order to achieve the above purpose, the invention adopts the technical scheme that:

a natural rubber antistatic insole containing graphene additives comprises the following basic components in parts by weight: 60-80 parts of natural rubber, 15-25 parts of POE (polyolefin elastomer), 5-15 parts of ethylene propylene diene monomer, 2-8 parts of graphene, 4-8 parts of antistatic powder, 4-8 parts of zinc oxide, 1-3 parts of zinc stearate, 1-3 parts of stearic acid, 0.5-2.0 parts of odorless cross-linking agent and 2-6 parts of foaming agent.

In order to better realize the invention, further, the shoe pad material comprises the following raw materials in parts by weight: 70 parts of natural rubber, 20 parts of POE (polyolefin elastomer), 10 parts of ethylene propylene diene monomer, 5 parts of graphene, 5 parts of antistatic powder, 6 parts of zinc oxide, 2 parts of zinc stearate, 2 parts of stearic acid, 1.0 part of odorless cross-linking agent and 4 parts of foaming agent.

In order to better implement the present invention, further, the POE elastomer is one of an ethylene-octene copolymer, an ethylene-butene copolymer, and an ethylene-hexene copolymer.

In order to better realize the invention, further, the antistatic powder is one of ethoxylated aliphatic alkylamine, alkyl sodium sulfonate, alkyl imidazoline salt, polyethylene oxide and polyether ester amide.

In order to better implement the invention, further, the odorless crosslinking agent is di-tert-butylperoxydiisopropylbenzene; the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide.

A natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, heating the graphene treated by stearic acid, sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, and mixing, vulcanizing and cross-linking again to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

In order to better realize the method, the specific step of graphene treatment in the step 1 is to mix stearic acid and deionized water according to a weight ratio of 1-3: 100, heat the mixture to 100-160 ℃ after uniform mixing, slowly and gradually add the graphene, continuously stir the mixture during adding, and continuously stir the mixture for 1-3 hours after adding, wherein the adding amount of the graphene is 2-8 mg/ml, so that the stearic acid-treated graphene is obtained.

In order to better realize the invention, the mixing temperature in the step 1 is 120-160 ℃, and the mixing time is 3-6 h.

In order to better realize the method, further, during vulcanization crosslinking in the step 2, hot pressing is firstly carried out on a plate vulcanizing machine for 20-30 min at 120-160 ℃ and under the pressure of 8-10 Mpa, and then secondary vulcanization is carried out in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h, so that the graphene antistatic insole material is obtained.

Advantageous effects

The invention has the following beneficial effects:

(1) the material contains graphene which is used as a reinforcing material of rubber, the mechanical property of the rubber can be greatly improved by filling a small amount of the graphene, and the graphene can show good electrical and thermal characteristics of the rubber, so that the material is an ideal rubber nano material, and the elasticity, the toughness and the tearing resistance of the insole can be improved by adding the graphene into the insole; the POE elastomer has excellent low-temperature impact resistance, low specific gravity, cleanness, compatibility with various basic polymers, excellent flexibility and puncture resistance, excellent elongation and high elasticity, good light transmittance and excellent electric insulation performance.

(2) The material has an antistatic effect, and the antistatic powder used in the invention is an internal mixing type antistatic agent, which is a type of antistatic agent added into rubber in the processing process of products. The invention uses the antistatic agent to endow the material surface with certain lubricity, reduce the friction coefficient, inhibit and reduce the generation of static charge, and has the characteristic of permanent antistatic.

(3) The insole preparation process of the invention firstly disperses the graphene in the rubber uniformly, the graphene is treated by stearic acid, and then the low-temperature impact resistance, low specific gravity and cleanness of the POE elastomer, which can be compatible with various basic polymers, the flexibility and puncture resistance are excellent, the elongation and high elasticity performance are excellent, the POE elastomer has good light transmittance and excellent electric insulation performance, and the vulcanization crosslinking is carried out, so that the obtained insole material has the advantages of antistatic property, antibiosis, deodorization, high elasticity, good wear resistance, strong toughness and tearing resistance, no toxicity, difficult deformation, easy cleaning and the like,

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

The embodiment provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials in parts by weight: 60 parts of natural rubber, 15 parts of POE (polyolefin elastomer), 5 parts of ethylene propylene diene monomer, 2 parts of graphene, 4 parts of antistatic powder, 4 parts of zinc oxide, 1 part of zinc stearate, 1 part of stearic acid, 0.5 part of odorless cross-linking agent and 2 parts of foaming agent.

A preparation method of a natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, mixing stearic acid and deionized water according to a weight ratio of 1:100, heating to 120 ℃ after uniform mixing, slowly and gradually adding graphene, continuously stirring while adding, continuously stirring for 3 hours after adding, wherein the adding amount of the graphene is 2mg/ml, so as to obtain stearic acid-treated graphene, then sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll at a mixing temperature of 160 ℃ for 3 hours, so as to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, mixing, vulcanizing and cross-linking again, firstly, hot-pressing on a flat vulcanizing machine for 30min at 120 ℃ and under the pressure of 8Mpa, and then, carrying out secondary vulcanization in an oven under the vulcanization conditions of 175 ℃, 4 hours, 195 ℃, 3 hours, 215 ℃ and 2 hours to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

Example 2

The embodiment provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials in parts by weight: 65 parts of natural rubber, 18 parts of POE (polyolefin elastomer), 8 parts of ethylene propylene diene monomer, 3 parts of graphene, 5 parts of antistatic powder, 5 parts of zinc oxide, 2 parts of zinc stearate, 2 parts of stearic acid, 0.8 part of odorless cross-linking agent and 3 parts of foaming agent.

A preparation method of a natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, mixing stearic acid and deionized water according to a weight ratio of 2:100, heating to 130 ℃ after uniform mixing, slowly and gradually adding graphene, continuously stirring while adding, continuously stirring for 3 hours after adding, wherein the adding amount of the graphene is 3mg/ml, so as to obtain stearic acid-treated graphene, then sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll at the mixing temperature of 150 ℃ for 4 hours, so as to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, mixing, vulcanizing and cross-linking again, firstly, hot-pressing on a flat vulcanizing machine for 30min at 130 ℃ and under 10Mpa, and then, carrying out secondary vulcanization in an oven under the vulcanization conditions of 180 ℃, 3 hours, 200 ℃, 3 hours, 220 ℃ and 2 hours to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

Example 3

The embodiment provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials in parts by weight: 70 parts of natural rubber, 20 parts of POE (polyolefin elastomer), 10 parts of ethylene propylene diene monomer, 5 parts of graphene, 5 parts of antistatic powder, 6 parts of zinc oxide, 2 parts of zinc stearate, 2 parts of stearic acid, 1.0 part of odorless cross-linking agent and 4 parts of foaming agent.

A preparation method of a natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, mixing stearic acid and deionized water according to a weight ratio of 2:100, heating to 150 ℃ after uniform mixing, slowly and gradually adding graphene, continuously stirring while adding, continuously stirring for 2 hours after adding, wherein the adding amount of the graphene is 5mg/ml, so as to obtain stearic acid-treated graphene, then sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll at the mixing temperature of 150 ℃ for 4 hours, so as to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, mixing, vulcanizing and cross-linking again, firstly, hot-pressing for 25min on a flat vulcanizing machine at 140 ℃ and under 10Mpa, and then, carrying out secondary vulcanization in an oven under the vulcanizing conditions of 180 ℃, 3 hours, 200 ℃, 2.5 hours, 220 ℃ and 1.5 hours to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

Example 4

The embodiment provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials in parts by weight: 75 parts of natural rubber, 22 parts of POE (polyolefin elastomer), 12 parts of ethylene propylene diene monomer, 6 parts of graphene, 6 parts of antistatic powder, 6 parts of zinc oxide, 2 parts of zinc stearate, 3 parts of stearic acid, 1.8 parts of odorless cross-linking agent and 5 parts of foaming agent.

A preparation method of a natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, mixing stearic acid and deionized water according to a weight ratio of 3:100, heating to 120 ℃ after uniform mixing, slowly and gradually adding graphene, continuously stirring while adding, continuously stirring for 3 hours after adding, wherein the adding amount of the graphene is 6mg/ml, so as to obtain stearic acid-treated graphene, then sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll at a mixing temperature of 140 ℃ for 5 hours, so as to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, tasteless cross-linking agent and foaming agent into the mixed virgin rubber, mixing, vulcanizing and cross-linking again, firstly, hot-pressing for 20min on a flat vulcanizing machine at 150 ℃ and under the pressure of 9Mpa, and then, carrying out secondary vulcanization in an oven under the vulcanization conditions of 183 ℃, 3h, 200 ℃, 2h, 220 ℃ and 1.5h to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

Example 5

The embodiment provides a natural rubber antistatic insole containing graphene additives, which comprises the following raw materials in parts by weight: 80 parts of natural rubber, 25 parts of POE (polyolefin elastomer), 15 parts of ethylene propylene diene monomer, 8 parts of graphene, 8 parts of antistatic powder, 8 parts of zinc oxide, 3 parts of zinc stearate, 3 parts of stearic acid, 2.0 parts of odorless cross-linking agent and 6 parts of foaming agent.

A preparation method of a natural rubber antistatic insole containing graphene additives comprises the following steps:

step 1, mixing stearic acid and deionized water according to a weight ratio of 3:100, heating to 130 ℃ after uniform mixing, slowly and gradually adding graphene, continuously stirring while adding, continuously stirring for 2 hours after adding, wherein the adding amount of the graphene is 8mg/ml, so as to obtain stearic acid-treated graphene, then sequentially adding natural rubber, POE (polyolefin elastomer) and ethylene propylene diene monomer, and mixing in a mixing roll at the mixing temperature of 130 ℃ for 4 hours, so as to obtain mixed virgin rubber;

step 2, adding antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, mixing, vulcanizing and cross-linking again, firstly, hot-pressing for 20min on a flat vulcanizing machine at 160 ℃ and under the pressure of 8Mpa, and then, carrying out secondary vulcanization in an oven under the vulcanization conditions of 185 ℃, 2h, 205 ℃, 2h, 225 ℃ and 1h to obtain the graphene antistatic insole material;

and 3, cutting the insole material into corresponding size and thickness according to the requirement to obtain the graphene additive natural antistatic insole.

The mechanical properties of the natural rubber antistatic insoles containing the graphene additives prepared in the above examples 1 to 5 were tested according to the following methods:

(1) and (4) detecting the volume resistivity and the surface conductivity according to a GB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.

(2) Tear strength: according to GB 6039-85, the tear strength is defined as: stretching the sample in the direction parallel to the main shaft of the sample until the maximum force is generated during cracking, preparing the sample according to the methods of GB529 and GB530, and standing the vulcanized test piece (the thickness is 2.0 +/-0.3 mm) in the testing step (1) at the standard room temperature (not less than 6 hours and not more than 15 days); (2) when a sample is taken, the direction of the bisector of the tearing angle of the cutter is consistent with the rolling direction; (3) vertically clamping the sample on an upper clamp and a lower clamp, and fully and uniformly clamping the sample at equal positions; (4) the tester is started after the stretching speed is adjusted (the tester is operated in a clamping device at the speed of 500 +/-100 mm/min), and then a gradually increased traction force can be applied to the test sample until the test sample is stopped after being torn off.

(3) Tensile strength: the procedure was followed according to ASTM D-412.

The test results were as follows:

TABLE 1 test results

Test results	Example 1	Example 2	Example 3	Example 4	Example 5
						Volume resistivity Ω · m	1014	1014	1014	1014	1014
Surface resistivity omega	1015	1015	1015	1015	1015
						Tear Strength kN/m	88	100	108	103	98
Tensile strength Mpa	43	44	48	47	45

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.