CN110964240B - Wear-resistant flame-retardant foam material for shoes and preparation method thereof - Google Patents
Wear-resistant flame-retardant foam material for shoes and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention discloses a wear-resistant flame-retardant foam material for shoes and a preparation method thereof, and belongs to the technical field of polymer composite foam materials. The foam material comprises the following raw material components: ethylene-vinyl acetate copolymer EVA, maleic anhydride grafted EVA, ethylene-octene copolymer, wear-resistant flame retardant, naphthenic oil, foaming agent, accelerator, stearic acid, zinc stearate, zinc oxide, dicumyl peroxide and antioxidant. The wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material. The wear-resistant flame-retardant foam material for shoes, which is prepared by the invention, has the advantages of good wear resistance, excellent flame-retardant effect, good processability and mechanical property, simple manufacturing process operation, energy conservation, environmental protection, and wide application prospect and market demand in practical application.
Description
Technical Field
The invention belongs to the technical field of polymer composite foam materials, and particularly relates to a wear-resistant flame-retardant foam material for shoes and a preparation method thereof.
Background
EVA is a thermoplastic plastic similar to rubber, and has good flexibility, rubber-like elasticity, excellent comprehensive physical and mechanical properties and good processability. The EVA foam material is a non-toxic, low-density, high-elasticity, high-specific-strength foam material, has good load-absorbing ability, and is therefore widely used as various sole materials. However, the EVA foaming material is often poor in wear resistance, and EVA is extremely easy to burn and has dense smoke and pungent smell during burning, so that a hot spot is formed by exploring a novel environment-friendly EVA composite material for expanding the application range of the EVA material.
Zinc Hexahydroxystannate (ZHS) is a novel green flame retardant, has the advantages of no toxicity, stability, high efficiency and excellent flame retardant property, and is increasingly paid more attention by people. Research shows that zinc hexahydroxystannate has good flame retardant performance in most high molecular materials, such as polyvinyl chloride, soft polyvinyl chloride, polyester, epoxy resin and the like. However, when the inorganic flame retardant is used to achieve a good flame retardant effect, the inorganic flame retardant needs to be added in a large amount and has poor compatibility with the polymer. By compounding different flame retardants, a synergistic flame-retardant effect is generated, so that the cost can be reduced, and more excellent flame-retardant performance can be obtained.
EVA is used as a polymer material with wide application, and a large amount of filler is required to be added in practical use to improve various properties of the EVA. The steel slag is waste slag generated in metallurgical industry, and contains a large amount of available components such as slag steel, calcium oxide, iron, magnesium oxide and the like. The steel slag is not unusable solid waste, and it is necessary and urgent to select a proper treatment process and a utilization way to develop the recycling value of the steel slag. The EVA material is commonly used as reinforcing filler such as talcum powder, calcium powder and carbon black, and the steel slag is used as an environment-friendly material to replace the reinforcing material, so that the environmental pollution can be reduced, the resource can be saved, the recycling of industrial waste can be realized, and the current industrial development requirements of energy conservation and emission reduction can be met.
Disclosure of Invention
The invention aims to provide a wear-resistant flame-retardant foam material for shoes and a preparation method thereof aiming at the defects of the prior art. Compared with the traditional foam material, the wear-resistant flame-retardant foam material for shoes, disclosed by the invention, has the advantages that the wear resistance and the flame retardant property of the EVA foam composite material are improved, better mechanical properties are provided, the use of carbon black is reduced, the environment pollution is reduced, and the wear-resistant flame-retardant foam material for shoes has wide application prospects and market demands.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the wear-resistant flame-retardant foam material for the shoes comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer EVA70-80 parts, maleic anhydride grafted EVA5-10 parts, ethylene-octene copolymer 5-10 parts, wear-resistant flame retardant 5-30 parts, naphthenic oil 2-3 parts, foaming agent AC 2-3 parts, accelerator 1-2 parts, stearic acid 1-2 parts, zinc stearate 1-2 parts, zinc oxide 3-5 parts, dicumyl peroxide 1-3 parts, and antioxidant 1-2 parts.
According to the wear-resistant flame-retardant foam material for shoes, the accelerator in the raw materials is tetramethyl thiuram disulfide, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material.
Further, the preparation method of the zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain modified steel slag;
3) preparation of zinc hexahydroxystannate coated modified steel slag: and (3) dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
A preparation method of the wear-resistant flame-retardant foam material for shoes comprises the following steps:
1) putting ethylene-vinyl acetate copolymer EVA into a torque rheometer for mixing according to raw material composition, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, accelerator, dicumyl peroxide, antioxidant, naphthenic oil, wear-resistant flame retardant and foaming agent, and mixing for 15-20 min;
2) placing the mixed material prepared in the step 1) at room temperature for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 3-5mm slices;
3) weighing the sheet prepared in the step 2) according to the volume of the mould, placing the sheet into a preheated mould cavity of a plate vulcanizing machine, and carrying out mould pressing and foaming for 8-10min at the temperature of 170-180 ℃ under the pressure of 10-15MPa to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
The wear-resistant flame retardant for the foam material for shoes is prepared by coating the modified steel slag with the zinc hexahydroxystannate, and the method is simple and convenient. The steel slag is used as waste material in metallurgical industry, has different grain sizes and has poor compatibility with polymers such as EVA and the like. The steel slag is modified by the titanate coupling agent HY-201, the surface structure of the steel slag can be effectively improved, and oleophylic groups are connected to the surface of the modified steel slag, so that the compatibility of the modified steel slag and a polymer is improved, a reinforcing effect is better achieved, and the abrasion is reduced. The zinc hexahydroxystannate can form a coupling reaction with HY-201 alkoxy on the modified steel slag through active hydroxyl, and can also be combined with phosphate ester generated after hydrolysis of HY-201 pyrophosphoric acid, so that the zinc hexahydroxystannate is coated on the modified steel slag in a chemical combination mode to form a novel composite material.
When the zinc hexahydroxystannate is heated and decomposed, water molecules are released to absorb heat, and the oxygen concentration is diluted. While Zn in zinc hexahydroxystannate2+And Sn4+The crosslinking of polyene structure in the EVA is promoted in the combustion process to further form a carbon layer, and the carbon layer and the metal oxide in the steel slag jointly form a compact heat insulation layer. In addition, HY-201 has a large number of long chains, so that the compatibility with polymer foam is improved, the processing technology is improved, the mechanical property of the composite material is enhanced, and the wear resistance of the foam composite material is improved.
The invention has the beneficial effects that:
the invention provides a wear-resistant flame-retardant foam material for shoes and a preparation method thereof. Meanwhile, waste residues generated in the metallurgical industry and zinc hexahydroxystannate are compounded to serve as functional fillers, so that the use of common fillers such as carbon black and the like is avoided, the environmental pollution is reduced, the resources are saved, the recycling of industrial wastes is realized, and the application range of the foam material is expanded.
Drawings
FIG. 1 is an SEM image of a quenched cross section of a composite foam material prepared by adding 20 parts of zinc hexahydroxystannate-coated modified steel slag in example 3.
FIG. 2 is an SEM image of a cross-section of a composite foam material prepared by adding 20 parts of steel slag in comparative example 2.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
The wear-resistant flame-retardant foam material for the shoes comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer EVA70 parts, maleic anhydride grafted EVA5 parts, ethylene-octene copolymer 10 parts, wear-resistant flame retardant 5 parts, naphthenic oil 2 parts, foaming agent AC 2.5 parts, accelerator 1 part, stearic acid 1 part, zinc stearate 1.5 parts, zinc oxide 4 parts, dicumyl peroxide 1 part and antioxidant 1 part.
The accelerator is tetramethyl thiuram disulfide, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol. The wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material.
The preparation method of the wear-resistant flame retardant zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain the modified steel slag.
3) Preparation of zinc hexahydroxystannate coated modified steel slag: and (3) dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
A preparation method of the wear-resistant flame-retardant foam material for shoes comprises the following steps:
(1) putting ethylene-vinyl acetate copolymer EVA into a torque rheometer for mixing according to raw material composition, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, accelerator, dicumyl peroxide, antioxidant, naphthenic oil, wear-resistant flame retardant and foaming agent, and mixing for 15 min;
(2) placing the mixed material prepared in the step (1) for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 3mm slices;
(3) weighing 50g of the sheet prepared in the step 5) according to the volume of the mould, placing the sheet into a preheated press vulcanizer mould cavity, and carrying out mould pressing foaming at 10MPa and 170 ℃ for 8min to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
Example 2
The wear-resistant flame-retardant foam material for shoes comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer EVA70 parts, maleic anhydride grafted EVA5 parts, ethylene-octene copolymer 10 parts, wear-resistant flame retardant 10 parts, naphthenic oil 2 parts, foaming agent AC 2.5 parts, accelerator 1 part, stearic acid 1 part, zinc stearate 1.5 parts, zinc oxide 4 parts, dicumyl peroxide 1 part and antioxidant 1 part.
The accelerator is tetramethyl thiuram disulfide, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol. The wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material.
The preparation method of the wear-resistant flame retardant zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain modified steel slag;
3) preparation of zinc hexahydroxystannate coated modified steel slag: dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
A preparation method of the wear-resistant flame-retardant foam material for shoes comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, a wear-resistant flame retardant, a foaming agent and the like, and mixing for 20 min;
(2) placing the mixed material prepared in the step (1) for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 5mm slices;
(3) weighing 50g of the sheet prepared in the step 5) according to the volume of the mould, placing the sheet in a preheated press vulcanizer mould cavity, and carrying out mould pressing foaming at 15MPa and 180 ℃ for 8min to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
Example 3
The wear-resistant flame-retardant foam material for shoes comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer EVA70 parts, maleic anhydride grafted EVA5 parts, ethylene-octene copolymer 10 parts, wear-resistant flame retardant 20 parts, naphthenic oil 2 parts, foaming agent AC 2.5 parts, accelerator 1 part, stearic acid 1 part, zinc stearate 1.5 parts, zinc oxide 4 parts, dicumyl peroxide 1 part and antioxidant 1 part.
The accelerator is tetramethyl thiuram disulfide, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol. The wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material.
The preparation method of the wear-resistant flame retardant zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain modified steel slag;
3) preparation of zinc hexahydroxystannate coated modified steel slag: dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
A preparation method of the wear-resistant flame-retardant foam material for shoes comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, a wear-resistant flame retardant, a foaming agent and the like, and mixing for 18 min;
(2) placing the mixed material prepared in the step (1) for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 4mm slices;
(3) weighing 50g of the sheet prepared in the step 5) according to the volume of the mould, placing the sheet in a preheated press vulcanizer mould cavity, and carrying out mould pressing foaming at the temperature of 175 ℃ under 13MPa for 8min to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
Example 4
The wear-resistant flame-retardant foam material for the shoes comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer EVA70 parts, maleic anhydride grafted EVA5 parts, ethylene-octene copolymer 10 parts, wear-resistant flame retardant 30 parts, naphthenic oil 2 parts, foaming agent AC 2.5 parts, accelerator 1 part, stearic acid 1 part, zinc stearate 1.5 parts, zinc oxide 4 parts, dicumyl peroxide 1 part and antioxidant 1 part.
The accelerator is tetramethyl thiuram disulfide, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.
The wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material.
The preparation method of the wear-resistant flame retardant zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain modified steel slag;
3) preparation of zinc hexahydroxystannate coated modified steel slag: dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
A preparation method of the wear-resistant flame-retardant foam material for shoes comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, a wear-resistant flame retardant, a foaming agent and the like, and mixing for 16 min;
(2) placing the mixed material prepared in the step (1) for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 5mm slices;
(3) weighing 50g of the sheet prepared in the step 5) according to the volume of the mould, placing the sheet into a preheated press vulcanizer mould cavity, and carrying out mould pressing foaming at 15MPa and 170 ℃ for 8min to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
Comparative example 1
An EVA foam composite material comprises the following raw materials in parts by weight: 70 parts of ethylene-vinyl acetate copolymer, 5 parts of maleic anhydride grafted EVA, 10 parts of ethylene-octene copolymer, 2 parts of naphthenic oil, 2.5 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 1.5 parts of zinc stearate, 4 parts of zinc oxide, 1 part of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
A preparation method of an EVA foam composite material comprises the following steps:
1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil and a foaming agent, and mixing for 15 min;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 15min, and pressing the mixture into 3mm slices;
3) weighing 50g of the sheet prepared in the step 2) according to the volume of the mould, placing the sheet in a preheated mould cavity of a flat vulcanizing machine, and carrying out mould pressing foaming for 8min at the temperature of 175 ℃ under the pressure of 10MPa to obtain the EVA foam composite material.
Comparative example 2
An EVA foam composite material comprises the following raw materials in parts by weight: 70 parts of ethylene-vinyl acetate copolymer, 5 parts of maleic anhydride grafted EVA, 10 parts of ethylene-octene copolymer, 20 parts of steel slag, 2 parts of naphthenic oil, 2.5 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 1.5 parts of zinc stearate, 4 parts of zinc oxide, 1 part of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
A preparation method of an EVA foam composite material comprises the following steps:
1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, steel slag and a foaming agent, and mixing for 15-20 min;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 15min, and pressing the mixture into 3-5mm slices;
3) weighing a certain mass of the sheet prepared in the step 2) according to the volume of the mould, placing the sheet into a preheated mould cavity of a flat vulcanizing machine, and carrying out mould pressing foaming at the temperature of 170 ℃ for 8min under the pressure of 10MPa to obtain the EVA foam composite material.
Comparative example 3
An EVA foam composite material comprises the following raw materials in parts by weight: 70 parts of ethylene-vinyl acetate copolymer, 5 parts of maleic anhydride grafted EVA, 10 parts of ethylene-octene copolymer, 20 parts of zinc hexahydroxystannate, 2 parts of naphthenic oil, 2.5 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 1.5 parts of zinc stearate, 4 parts of zinc oxide, 1 part of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
A preparation method of an EVA foam composite material comprises the following steps:
1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, zinc hexahydroxystannate, a foaming agent and the like, and mixing for 15-20 min;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 15min, and pressing the mixture into 3-5mm slices;
3) weighing a certain mass of the sheet prepared in the step 2) according to the volume of the mould, placing the sheet in a preheated mould cavity of a flat vulcanizing machine, and carrying out mould pressing foaming at the temperature of 175 ℃ for 8min under the pressure of 10MPa to obtain the EVA foam composite material.
Comparative example 4
An EVA foam composite material comprises the following raw materials in parts by weight: 70 parts of ethylene-vinyl acetate copolymer, 5 parts of maleic anhydride grafted EVA, 10 parts of ethylene-octene copolymer, 18.2 parts of modified steel slag, 1.8 parts of zinc hexahydroxystannate, 2 parts of naphthenic oil, 2.5 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 1.5 parts of zinc stearate, 4 parts of zinc oxide, 1 part of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
The preparation method of the modified steel slag comprises the following steps:
1) steel slag pretreatment: putting a certain amount of steel slag powder into a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: dissolving absolute ethyl alcohol and deionized water in a volume ratio of 9:1 in a three-neck flask, uniformly mixing, adding 1ml of titanate coupling agent HY-201, ultrasonically dispersing for 60min, adding 20g of ball-milled steel slag powder into the flask, stirring and reacting for 4h at 80 ℃, washing and drying to obtain the modified steel slag.
A preparation method of an EVA foam composite material comprises the following steps:
1) mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, naphthenic oil, modified steel slag, zinc hexahydroxystannate, a foaming agent and the like, and mixing for 15-20 min;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 15min, and pressing the mixture into 3-5mm slices;
3) weighing a certain mass of the sheet prepared in the step 2) according to the volume of the mould, placing the sheet in a preheated mould cavity of a flat vulcanizing machine, and carrying out mould pressing foaming at the temperature of 175 ℃ for 8min under the pressure of 10MPa to obtain the EVA foam composite material.
The EVA foam composites obtained from examples 1-4 and comparative example 1 were subjected to comparative performance tests, and the results are shown in Table 1.
Table 1 comparative testing of properties
Example 3 SEM image of the cross section of the composite foam material with 20 parts of zinc hexahydroxystannate coated and modified steel slag is shown in figure 1; comparative example 2 SEM image of the cross-section of a composite foam with 20 parts of steel slag added is shown in FIG. 2. Comparing fig. 1 and fig. 2, the results show that: FIG. 2 clearly shows that there are many bare steel slag particles on the cross section, i.e. the unmodified steel slag has poor compatibility with the composite foam material; the section of the section in FIG. 1 is flat compared with that of FIG. 2, and the added filler is uniformly dispersed in the polymer matrix, so that the two are better in compatibility.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. The wear-resistant flame-retardant foam material for shoes is characterized in that: the raw materials comprise the following components in parts by weight: ethylene-vinyl acetate copolymer EVA70-80 parts, maleic anhydride grafted EVA5-10 parts, ethylene-octene copolymer 5-10 parts, wear-resistant flame retardant 5-30 parts, naphthenic oil 2-3 parts, foaming agent AC 2-3 parts, accelerator 1-2 parts, stearic acid 1-2 parts, zinc stearate 1-2 parts, zinc oxide 3-5 parts, dicumyl peroxide 1-3 parts, and antioxidant 1-2 parts; the wear-resistant flame retardant is a zinc hexahydroxystannate coated modified steel slag composite material;
the preparation method of the wear-resistant flame retardant zinc hexahydroxystannate coated modified steel slag composite material comprises the following steps:
1) steel slag pretreatment: taking 50g of steel slag powder in a ball mill, adding 150ml of absolute ethyl alcohol, ball-milling for 12 hours, and drying for later use;
2) preparation of modified steel slag: 100ml of absolute ethyl alcohol and deionized water in a volume ratio of 9:1 are uniformly mixed in a three-neck flask, 1ml of titanate coupling agent HY-201 is added, ultrasonic dispersion is carried out for 60min, 20g of ball-milled steel slag powder is added into the flask, stirring reaction is carried out for 4h at 80 ℃, and washing and drying are carried out to obtain modified steel slag;
3) preparation of zinc hexahydroxystannate coated modified steel slag: and (3) dissolving 5g of the modified steel slag prepared in the step 2) in 100ml of 50% ethanol aqueous solution, adding 0.5g of zinc hexahydroxystannate, violently stirring at 85 ℃ for reacting for 4h, and performing suction filtration, washing and drying to obtain the zinc hexahydroxystannate coated modified steel slag composite material.
2. A wear resistant flame retardant foam material for shoes as claimed in claim 1 wherein: the accelerator is tetramethyl thiuram disulfide, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.
3. A method of making an abrasion resistant flame retardant foam for shoes as claimed in any of claims 1-2, characterized in that: the method comprises the following steps:
1) putting ethylene-vinyl acetate copolymer EVA into a torque rheometer for mixing according to raw material components, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, accelerant, dicumyl peroxide, antioxidant, naphthenic oil, wear-resistant flame retardant and foaming agent, and mixing for 15-20 min;
2) placing the mixed material prepared in the step 1) for 24 hours, then placing the mixed material into an open mill for mixing for 15min, and pressing the mixed material into 3-5mm slices;
3) weighing 50g of sheet prepared in the step 2) according to the volume of the mould, placing the sheet in a preheated mould cavity of a flat vulcanizing machine, and carrying out mould pressing and foaming for 8-10min at the temperature of 170-180 ℃ under the pressure of 10-15MPa to obtain the environment-friendly wear-resistant flame-retardant EVA foam composite material.
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| CN103450544A (en) * | 2013-08-07 | 2013-12-18 | 合肥安聚达新材料科技有限公司 | Low-smoke, halogen-free and flame-retardant irradiation crosslinking polyolefin composite material and preparation method thereof |
| CN103804775A (en) * | 2014-03-06 | 2014-05-21 | 福州大学 | Halogen-free flame-retardant polyolefin composite foam material and preparation method thereof |
| CN108976588A (en) * | 2018-08-02 | 2018-12-11 | 福州大学 | A kind of flame-retardant and anti-static eva foam composite material and preparation method |
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| CN103804775A (en) * | 2014-03-06 | 2014-05-21 | 福州大学 | Halogen-free flame-retardant polyolefin composite foam material and preparation method thereof |
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