CN110845817A - Environment-friendly rubber sole and production process thereof - Google Patents
Environment-friendly rubber sole and production process thereof Download PDFInfo
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- CN110845817A CN110845817A CN201911178804.XA CN201911178804A CN110845817A CN 110845817 A CN110845817 A CN 110845817A CN 201911178804 A CN201911178804 A CN 201911178804A CN 110845817 A CN110845817 A CN 110845817A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
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.
Description
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.
Example 1
An environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 8 parts of natural rubber, 16 parts of butadiene styrene rubber, 20 parts of butadiene rubber, 15 parts of white carbon black, 1.3 parts of diethylene glycol, 1.0 part of white oil, 2.3 parts of zinc oxide, 0.3 part of stearic acid, PEG-40001.0 parts, 0.7 part of anti-aging agent, 0.3 part of anti-fog wax, 1.2 parts of antioxidant, 0.5 part of vulcanization accelerator DM, 0.2 part of vulcanization accelerator M, 0.8 part of vulcanizing agent, 0.6 part of bridging agent and 0.06 part of TS accelerator.
The production process of the environment-friendly rubber sole comprises the following steps:
s1, adding natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, white 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 118 ℃, 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, and controlling the vulcanizing temperature to be 150 ℃, the vulcanizing pressure to be 14.5MPa and the vulcanizing time to be 200S to obtain 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 anti-aging agent is an anti-aging agent RD.
The antioxidant is antioxidant 168.
The vulcanizing agent is formed by mixing 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide according to a mass ratio of (6-13): 1.
The bridging agent is zinc acrylate.
Comparative example 1
An environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 8 parts of natural rubber, 16 parts of butadiene styrene rubber, 20 parts of butadiene rubber, 15 parts of white carbon black, 1.3 parts of diethylene glycol, 1.0 part of palm oil, 2.3 parts of zinc oxide, 0.3 part of stearic acid, PEG-40001.0 parts, 0.7 part of anti-aging agent, 0.3 part of anti-fog wax, 1.2 parts of antioxidant, 0.5 part of vulcanization accelerator DM, 0.2 part of vulcanization accelerator M, 0.8 part of vulcanizing agent, 0.6 part of bridging agent and 0.06 part of TS accelerator.
The production process of the environment-friendly rubber sole comprises the following steps:
s1, adding natural rubber, styrene butadiene rubber, white carbon black, diethylene glycol, 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 118 ℃, 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, and controlling the vulcanizing temperature to be 150 ℃, the vulcanizing pressure to be 14.5MPa and the vulcanizing time to be 200S to obtain 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 anti-aging agent is an anti-aging agent RD.
The antioxidant is antioxidant 168.
The vulcanizing agent is formed by mixing 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide according to a mass ratio of (6-13): 1.
The bridging agent is zinc acrylate.
Example 2
An environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 8 parts of natural rubber, 16 parts of butadiene styrene rubber, 20 parts of butadiene rubber, 15 parts of white carbon black, 1.3 parts of diethylene glycol, 1.0 part of epoxy palm oil, 2.3 parts of zinc oxide, 0.3 part of stearic acid, PEG-40001.0 parts, 0.7 part of anti-aging agent, 0.3 part of anti-fog wax, 1.2 parts of antioxidant, 0.5 part of vulcanization accelerator DM, 0.2 part of vulcanization accelerator M, 0.8 part of vulcanizing agent, 0.6 part of bridging agent and 0.06 part of TS accelerator.
The production process of the environment-friendly rubber sole 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 118 ℃, 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, and controlling the vulcanizing temperature to be 150 ℃, the vulcanizing pressure to be 14.5MPa and the vulcanizing time to be 200S to obtain 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 preparation method of the epoxy palm oil comprises the following steps: uniformly stirring and mixing 100g of palm oil, 20g of formic acid and 1g of concentrated sulfuric acid, dropwise adding 140g of 30 wt% aqueous hydrogen peroxide solution at 45 ℃ and 200rpm, and finishing dropwise adding within 50-60 minutes; then keeping the temperature at 70 ℃ for 9 h; and (3) standing and layering, taking the upper oily liquid, washing the upper oily liquid with 0.10mol/L sodium hydroxide aqueous solution for three times, washing the upper oily liquid with water to be neutral, and dehydrating to obtain the epoxy palm oil.
The anti-aging agent is an anti-aging agent RD.
The antioxidant is antioxidant 168.
The vulcanizing agent is formed by mixing 2-acrylamide-2-methylpropanesulfonic acid and dicumyl peroxide according to a mass ratio of (6-13): 1.
The bridging agent is zinc acrylate.
Comparative example 2
An environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 8 parts of natural rubber, 16 parts of butadiene styrene rubber, 20 parts of butadiene rubber, 15 parts of white carbon black, 1.3 parts of diethylene glycol, 1.0 part of epoxy palm oil, 2.3 parts of zinc oxide, 0.3 part of stearic acid, PEG-40001.0 parts, 0.7 part of anti-aging agent, 0.3 part of anti-fog wax, 1.2 parts of antioxidant, 0.5 part of vulcanization accelerator DM, 0.2 part of vulcanization accelerator M, 0.8 part of sulfur, 0.6 part of bridging agent and 0.06 part of TS accelerator.
The production process of the environment-friendly rubber sole 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 118 ℃, 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, and controlling the vulcanizing temperature to be 150 ℃, the vulcanizing pressure to be 14.5MPa and the vulcanizing time to be 200S to obtain 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 preparation method of the epoxy palm oil comprises the following steps: uniformly stirring and mixing 100g of palm oil, 20g of formic acid and 1g of concentrated sulfuric acid, dropwise adding 140g of 30 wt% aqueous hydrogen peroxide solution at 45 ℃ and 200rpm, and finishing dropwise adding within 50-60 minutes; then keeping the temperature at 70 ℃ for 9 h; and (3) standing and layering, taking the upper oily liquid, washing the upper oily liquid with 0.10mol/L sodium hydroxide aqueous solution for three times, washing the upper oily liquid with water to be neutral, and dehydrating to obtain the epoxy palm oil.
The anti-aging agent is an anti-aging agent RD.
The antioxidant is antioxidant 168.
The bridging agent is zinc acrylate.
Comparative example 3
An environment-friendly rubber sole is prepared from the following raw materials in parts by weight: 8 parts of natural rubber, 16 parts of butadiene styrene rubber, 20 parts of butadiene rubber, 15 parts of white carbon black, 1.3 parts of diethylene glycol, 1.0 part of epoxy palm oil, 2.3 parts of zinc oxide, 0.3 part of stearic acid, PEG-40001.0 parts, 0.7 part of anti-aging agent, 0.3 part of anti-fog wax, 1.2 parts of antioxidant, 0.5 part of vulcanization accelerator DM, 0.2 part of vulcanization accelerator M, 0.8 part of vulcanizing agent, 0.6 part of bridging agent and 0.06 part of TS accelerator.
The production process of the environment-friendly rubber sole 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 118 ℃, 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, and controlling the vulcanizing temperature to be 150 ℃, the vulcanizing pressure to be 14.5MPa and the vulcanizing time to be 200S to obtain 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 preparation method of the epoxy palm oil comprises the following steps: uniformly stirring and mixing 100g of palm oil, 20g of formic acid and 1g of concentrated sulfuric acid, dropwise adding 140g of 30 wt% aqueous hydrogen peroxide solution at 45 ℃ and 200rpm, and finishing dropwise adding within 50-60 minutes; then keeping the temperature at 70 ℃ for 9 h; and (3) standing and layering, taking the upper oily liquid, washing the upper oily liquid with 0.10mol/L sodium hydroxide aqueous solution for three times, washing the upper oily liquid with water to be neutral, and dehydrating to obtain the epoxy palm oil.
The anti-aging agent is an anti-aging agent RD.
The antioxidant is antioxidant 168.
The vulcanizing agent is dicumyl peroxide.
The bridging agent is zinc acrylate.
Test example 1
The wear resistance of the soles prepared in examples 1-2 and comparative examples 1-3 was tested, and the specific results are shown in table 1.
TABLE 1 abrasion resistance
The test results show that the wear resistance of the environment-friendly rubber sole prepared in the example 2 is obviously superior to that of the environment-friendly rubber sole prepared in the example 1 and the comparative examples 1-3; the reason for this is that: 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 and more stable chemical bonds are formed with a polymer, the wear resistance of the rubber sole is obviously improved, and the environmental protection of the processing aid is improved to a certain extent.
Test example 2
The tensile strength, the tear strength and the folding endurance of the soles prepared in the examples 1 to 2 and the comparative examples 1 to 3 were tested, and the specific results are shown in table 2.
TABLE 2 tensile Strength and abrasion resistance
The present invention has been described in detail, and the principle and embodiments of the present invention are explained herein by using specific examples, which are only used to help understand the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (9)
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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533967A (en) * | 2020-06-16 | 2020-08-14 | 广东石油化工学院 | Rubber sole and preparation method thereof |
| CN114685868A (en) * | 2022-04-13 | 2022-07-01 | 浙江碳足迹科技集团有限公司 | Environment-friendly shoe and preparation method thereof |
| CN115246961A (en) * | 2021-09-24 | 2022-10-28 | 上海年与轻科技(集团)有限公司 | Oil stain ground anti-skid rubber material for shoe soles and preparation method thereof |
| CN117683279A (en) * | 2024-02-02 | 2024-03-12 | 比音勒芬服饰股份有限公司 | Double-arch bridge type supporting shock-absorbing anti-skid sole and preparation method thereof |
| CN117887153A (en) * | 2024-01-31 | 2024-04-16 | 广州市政鑫橡塑有限公司 | Environment-friendly sole rubber composition and preparation method thereof |
-
2019
- 2019-11-27 CN CN201911178804.XA patent/CN110845817A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533967A (en) * | 2020-06-16 | 2020-08-14 | 广东石油化工学院 | Rubber sole and preparation method thereof |
| CN111533967B (en) * | 2020-06-16 | 2022-05-17 | 广东石油化工学院 | Rubber sole and preparation method thereof |
| CN115246961A (en) * | 2021-09-24 | 2022-10-28 | 上海年与轻科技(集团)有限公司 | Oil stain ground anti-skid rubber material for shoe soles and preparation method thereof |
| CN114685868A (en) * | 2022-04-13 | 2022-07-01 | 浙江碳足迹科技集团有限公司 | Environment-friendly shoe and preparation method thereof |
| CN117887153A (en) * | 2024-01-31 | 2024-04-16 | 广州市政鑫橡塑有限公司 | Environment-friendly sole rubber composition and preparation method thereof |
| CN117683279A (en) * | 2024-02-02 | 2024-03-12 | 比音勒芬服饰股份有限公司 | Double-arch bridge type supporting shock-absorbing anti-skid sole and preparation method thereof |
| CN117683279B (en) * | 2024-02-02 | 2024-04-05 | 比音勒芬服饰股份有限公司 | Double-arch bridge type supporting shock-absorbing anti-skid sole and preparation method thereof |
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