阅读说明：本技术 环保橡胶鞋底及其生产工艺 (Environment-friendly rubber sole and production process thereof ) 是由 李滨男 于 2019-11-27 设计创作，主要内容包括：本发明公开了一种环保橡胶鞋底及其生产工艺。所述环保橡胶鞋底由以下原料制备而成：天然橡胶、丁苯橡胶、顺丁橡胶、白炭黑、二甘醇、环氧棕榈油、氧化锌、硬脂酸、PEG-4000、防老剂、防雾蜡、抗氧剂、硫化促进剂DM、硫化促进剂M、硫化剂、架桥剂、TS促进剂。本发明通过对棕榈油进行环氧化处理,赋予了棕榈油更好的稳定性和官能团,提供了足够的反应性,能够与聚合物形成更多的化学键,实现对橡胶鞋底耐磨性能的提升。(The invention discloses an environment-friendly rubber sole and a production process thereof. The environment-friendly rubber sole is prepared from the following raw materials: natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, epoxy palm oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, antifogging wax, an antioxidant, a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator. According to the invention, the palm oil is subjected to epoxidation treatment, so that the palm oil is endowed with better stability and functional groups, sufficient reactivity is provided, more chemical bonds can be formed with polymers, and the improvement of the wear resistance of rubber soles is realized.)

1. The environment-friendly rubber sole is characterized by being prepared from the following raw materials: natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, white oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, anti-fog wax, an antioxidant, a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator.

2. The environment-friendly rubber sole is characterized by being prepared from the following raw materials: natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, epoxy palm oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, antifogging wax, an antioxidant, a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator.

3. The environment-friendly rubber sole as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 6-10 parts of natural rubber, 11-20 parts of styrene butadiene rubber, 15-25 parts of butadiene rubber, 12-18 parts of white carbon black, 1.0-1.5 parts of diethylene glycol, 0.8-1.5 parts of epoxy palm oil, 1.5-2.8 parts of zinc oxide, 0.1-0.5 part of stearic acid, 0.5-1.5 parts of PEG-40000.5, 0.5-1.0 part of anti-aging agent, 0.1-0.5 part of anti-fog wax, 1.0-2.0 parts of antioxidant, 0.2-0.6 part of vulcanization accelerator DM, 0.1-0.3 part of vulcanization accelerator M, 0.5-2.0 parts of vulcanizing agent, 0.3-1.8 parts of bridging agent and 0.05-0.1 part of TS accelerator.

4. The environment-friendly rubber sole as claimed in claim 3, wherein the epoxy palm oil is prepared by the following steps: uniformly mixing palm oil, formic acid and concentrated sulfuric acid according to a mass ratio of (13-26) to (0.3-2.0), dropwise adding 20-35 wt% of aqueous hydrogen peroxide under the conditions of 40-65 ℃ and 100-300 rpm, wherein the mass ratio of the aqueous hydrogen peroxide to the palm oil is (1.0-1.6) to 1, and dropwise adding is completed within 50-60 minutes; then keeping the temperature at 65-75 ℃ for 6-10 h; and standing for layering, taking the upper oily liquid, washing with alkali liquor, washing with water to be neutral, and dehydrating to obtain the epoxy palm oil.

5. The environment-friendly rubber sole as defined in claim 3, wherein the anti-aging agent is a mixture of one or more of anti-aging agent RD and anti-aging agent MB.

6. The environment-friendly rubber sole as claimed in claim 3, wherein the antioxidant is one or a mixture of several of antioxidant 168, antioxidant 1010 and antioxidant 1330.

7. The environment-friendly rubber sole according to claim 3, wherein the vulcanizing agent is formed by mixing 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide according to a mass ratio of (6-13): 1.

8. The environment-friendly rubber sole as claimed in claim 3, wherein the bridging agent is any one or more of triallyl isocyanurate, 1,3, 5-triallyl cyanurate and zinc acrylate.

9. The production process of the environment-friendly rubber sole as claimed in any one of claims 2 to 8, characterized by comprising the following steps:

s1, adding natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, epoxy palm oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, an anti-fog wax and an antioxidant into an internal mixer for internal mixing, discharging rubber at 110-120 ℃, standing at room temperature for 18-30 hours, then mixing on an open mill, adding a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator, and mixing uniformly to obtain a rubber sheet;

s2, placing the rubber sheet obtained in the step S1 in a preset sole mold, vulcanizing the rubber sheet in a vulcanizing machine, controlling the vulcanizing temperature to be 140-165 ℃, the vulcanizing pressure to be 14.0-15.5 MPa and the vulcanizing time to be 180-250S, and obtaining a crude product of the environment-friendly rubber sole;

s3, carrying out other post-treatment operations such as trimming, edging and painting on the crude product of the environment-friendly rubber sole to obtain the environment-friendly rubber sole.

Technical Field

The invention relates to an environment-friendly rubber sole and a production process thereof, and belongs to the technical field of rubber processing.

Background

Petroleum is a derivative of the petrochemical industry and is commonly used as a plasticizer for natural and synthetic rubbers in the tire industry. In petroleum, aromatic, naphthenic and paraffinic oils, white oils, and the like are often used as processing aids, with peroxides being the crosslinking agent. However, it is noteworthy that oil has been depleted and adversely affects human health. In response, there is an increasing need to find renewable, safe, sustainable and environmentally friendly alternative oils.

Vegetable oils are an attractive natural resource for the synthesis of bio-based polymers due to their stability, low cost, environmental friendliness and biodegradability. The vegetable oil is used as an excellent plasticizer and is used as a substitute of petrochemical derivatives in the plastic and rubber industries, and has very important environmental protection significance.

Palm oil is environmentally friendly, biodegradable, and a relatively low cost processing aid. Palm oil can exhibit better processability by enhancing the interaction between rubber and filler and dispersion as an eco-friendly processing aid. Although the application of palm oil as an eco-friendly processing aid in rubber processing can improve the strength of rubber products to some extent, the improvement in the wear resistance of rubber products is still far from enough, mainly because of the few functional groups capable of participating in the polymer reaction in palm oil.

According to the preparation method, double bonds in the palm oil are converted into epoxy bonds by adopting a novel preparation method, and higher epoxy conversion rate is provided, so that the reactivity of the palm oil is improved, more and more stable chemical bonds are formed with a polymer, and the improvement of the wear resistance of a rubber product is realized.

Disclosure of Invention

Aiming at the technical problems, the invention provides the environment-friendly rubber sole and the production process thereof, and the environment-friendly rubber sole is produced and processed by adopting environment-friendly epoxy palm oil to replace petroleum oil such as white oil.

Due to its stability, low cost, environmental friendliness and biodegradability, vegetable oils have a very significant application value as substitutes for petrochemical derivatives in the plastics and rubber industry. In the prior art, the strength of a rubber product can be improved to a certain extent by applying palm oil as an eco-friendly processing aid to rubber processing, but the improvement on the wear resistance of the rubber product is still far insufficient, mainly because the palm oil has fewer functional groups capable of participating in a polymer reaction. Therefore, the epoxy palm oil with high epoxidation conversion rate is prepared by the novel method, sufficient reactivity is provided, more chemical bonds can be formed with polymers, and the wear resistance of the rubber sole can be obviously enhanced.

The specific technical method comprises the following steps:

the invention discloses one of the technical schemes: an environment-friendly rubber sole is prepared from the following raw materials: natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, white oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, anti-fog wax, an antioxidant, a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator.

The second technical scheme disclosed by the invention is as follows: an environment-friendly rubber sole is prepared from the following raw materials: natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, epoxy palm oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, antifogging wax, an antioxidant, a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator. Further preferably, the environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 6-10 parts of natural rubber, 11-20 parts of styrene butadiene rubber, 15-25 parts of butadiene rubber, 12-18 parts of white carbon black, 1.0-1.5 parts of diethylene glycol, 0.8-1.5 parts of epoxy palm oil, 1.5-2.8 parts of zinc oxide, 0.1-0.5 part of stearic acid, 0.5-1.5 parts of PEG-40000.5, 0.5-1.0 part of anti-aging agent, 0.1-0.5 part of anti-fog wax, 1.0-2.0 parts of antioxidant, 0.2-0.6 part of vulcanization accelerator DM, 0.1-0.3 part of vulcanization accelerator M, 0.5-2.0 parts of vulcanizing agent, 0.3-1.8 parts of bridging agent and 0.05-0.1 part of TS accelerator.

Preferably, the preparation method of the epoxy palm oil comprises the following steps: uniformly mixing palm oil, formic acid and concentrated sulfuric acid according to a mass ratio of (13-26) to (0.3-2.0), dropwise adding 20-35 wt% of aqueous hydrogen peroxide under the conditions of 40-65 ℃ and 100-300 rpm, wherein the mass ratio of the aqueous hydrogen peroxide to the palm oil is (1.0-1.6) to 1, and dropwise adding is completed within 50-60 minutes; then keeping the temperature at 65-75 ℃ for 6-10 h; standing for layering, taking the upper oily liquid, washing with alkali liquor, washing with water to neutrality, and dehydrating to obtain the epoxy palm oil; the alkali liquor is 0.05-0.10 mol/L sodium hydroxide aqueous solution or 0.05-0.10 mol/L potassium hydroxide aqueous solution.

Preferably, the anti-aging agent is one or a mixture of anti-aging agents RD and MB.

Preferably, the antioxidant is one or a mixture of several of antioxidant 168, antioxidant 1010 and antioxidant 1330.

Preferably, the vulcanizing agent is formed by mixing 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide according to a mass ratio of (6-13): 1.

2-acrylamido-2-methylpropanesulfonic acid is a vinyl monomer having excellent radical polymerization reactivity and acidity, which is grafted onto rubber by dicumyl peroxide and then reacts with zinc oxide to form an ionic bond; compared with the common chemically crosslinked rubber, the degree of compactness of the rubber network can be obviously improved.

Preferably, the bridging agent is any one or a mixture of more of triallyl isocyanurate, 1,3, 5-triallyl cyanurate and zinc acrylate.

The invention also discloses a production process of the environment-friendly rubber sole, which comprises the following steps:

s1, adding natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, epoxy palm oil, zinc oxide, stearic acid, PEG-4000, an anti-aging agent, an anti-fog wax and an antioxidant into an internal mixer for internal mixing, discharging rubber at 116-120 ℃, standing at room temperature for 24 hours, then mixing on an open mill, adding a vulcanization accelerator DM, a vulcanization accelerator M, a vulcanizing agent, a bridging agent and a TS accelerator, and mixing uniformly to obtain a rubber sheet;

s2, placing the rubber sheet obtained in the step S1 in a preset sole mold, vulcanizing the rubber sheet in a vulcanizing machine, controlling the vulcanizing temperature to be 140-165 ℃, the vulcanizing pressure to be 14.0-15.5 MPa and the vulcanizing time to be 180-250S, and obtaining a crude product of the environment-friendly rubber sole;

s3, carrying out other post-treatment operations such as trimming, edging and painting on the crude product of the environment-friendly rubber sole to obtain the environment-friendly rubber sole.

The invention has the beneficial effects that:

(1) according to the invention, double bonds in the palm oil are converted into epoxy, so that higher epoxy conversion rate is realized, more active functional groups are provided, the reactivity of the palm oil is improved, more stable chemical bonds are formed with a polymer, and the wear resistance of the rubber sole is obviously improved;

(2) the invention further promotes the processing of the environment-friendly rubber sole by replacing unfriendly sulfur with environment-friendly vulcanizing agents (2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide); moreover, a novel vulcanizing agent, 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide are adopted, covalent bonds and ionic bonds are introduced to realize hybrid crosslinking, the crosslinking density and strength are improved, and finally the wear resistance of the rubber product is improved.

Detailed Description

Details of some of the raw materials in this example are as follows:

natural rubber: vietnam SVR-3L natural rubber.

Styrene-butadiene rubber: zilwite 1502 styrene butadiene rubber/SBR 1502.

Butadiene rubber: the model is as follows: yanshan petrochemical BR 9000.

White carbon black: the grain diameter is 200 meshes.

White oil: model 100, specific gravity 0.88, flash point 220 ℃.

Anti-aging agent RD: CAS number: 26780-96-1.

Anti-fog wax: is an antifogging agent HB-1956, Zhanlin chemical raw material Co.

Antioxidant 168: CAS number: 31570-04-4.

Vulcanization accelerator DM: 2, 2' -dibenzothiazyl disulfide, CAS No.: 120-78-5.

Vulcanization accelerator M: 2-mercaptobenzothiazole, CAS No.: 149-30-4.

Sulfur: the content is 99.92 wt%.

Zinc acrylate: CAS number: 14643-87-9.

TS accelerator: tetramethylthiuram monosulfide, CAS no: 97-74-5.