CN111333950A - High-mechanical-strength wear-resistant EVA composite foam material and preparation method thereof - Google Patents
High-mechanical-strength wear-resistant EVA composite foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-mechanical-strength wear-resistant EVA composite foam material and a preparation method thereof, wherein the foam material comprises the following components: ethylene-vinyl acetate copolymer, maleic anhydride grafted EVA, ethylene-octene copolymer, composite wear-resistant agent, rosin resin, naphthenic oil, foaming agent, accelerator, stearic acid, zinc stearate, zinc oxide, dicumyl peroxide and antioxidant. The composite wear-resistant agent is a modified white corundum/graphene oxide composite material. Compared with the traditional EVA foam material, the high-mechanical-strength wear-resistant EVA composite foam material prepared by the invention has the advantages of better mechanical property and wear resistance under the condition of less filler addition, better processing property, simple manufacturing process operation, energy conservation, environmental protection, wide application prospect in practical application and market demand.
Description
Technical Field
The invention belongs to the field of polymer composite foam materials, and particularly relates to a high-mechanical-strength wear-resistant EVA composite foam material and a preparation method thereof.
Background
Ethylene-vinyl acetate copolymer (EVA) is a thermoplastic plastic similar to rubber, and has better flexibility, obdurability, transparency and compatibility with filler than Polyethylene (PE), and the EVA has excellent comprehensive physical and mechanical properties and good processing performance. EVA foam materials have excellent resilience, flexibility, good foaming properties and load-absorbing ability at normal temperature, and thus are widely used as various sole materials. However, the EVA foaming material also has the problems of easy abrasion and short service life. Along with the development of the social and economic level and the progress of science and technology, the limitations of the traditional reinforcing filler are increasingly highlighted, and the exploration of novel environment-friendly functional fillers becomes a hotspot.
The white corundum is prepared by taking industrial alumina as a raw material and smelting at a high temperature, is white and contains a small amount of components such as ferric oxide, silicon oxide and the like. The white corundum has the characteristics of compact texture, high hardness, sharp-horn shape of grains, high purity, acid resistance, alkali resistance, corrosion resistance, high temperature resistance, good thermal stability and the like, is suitable for manufacturing a ceramic and resin consolidation grinding tool and grinding, polishing, sand blasting and the like, and can effectively improve the wear resistance of the material by adding the white corundum into a polymer.
Graphene Oxide (GO) is an important derivative of graphene, and has the characteristics of small size, large specific surface area, high strength, sheet-like structure, easiness in modification and the like. The surface of the graphene oxide is rich in oxygen-containing groups such as hydroxyl, carboxyl and the like, so that the graphene oxide is easily compatible with polymers such as EVA and the like, and the wear resistance, heat resistance and other properties of the polymers can be obviously improved by adding a small amount of the graphene oxide.
Disclosure of Invention
The invention aims to provide a preparation method of a high-mechanical-strength wear-resistant EVA composite foam material aiming at the defects of the prior art. Compared with the traditional EVA foam material, the high-mechanical-strength wear-resistant EVA composite foam material prepared by the invention has the advantages that under the condition of less filler addition amount, better mechanical property and wear resistance are obtained, better processing property is realized, the manufacturing process is simple to operate, wide application prospect and market demand are realized in practical application, and the application range of the EVA foam material is expanded.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a high-mechanical-strength wear-resistant EVA composite foam material comprises the following raw materials in parts by weight: 65-75 parts of ethylene-vinyl acetate copolymer, 10-20 parts of maleic anhydride grafted EVA (ethylene-vinyl acetate), 5-10 parts of ethylene-octene copolymer, 5-10 parts of rosin resin, 2-10 parts of composite wear-resistant agent, 2-4 parts of naphthenic oil, 3-5 parts of foaming agent AC, 1-2 parts of accelerator, 0.5-2 parts of stearic acid, 0.5-1.5 parts of zinc stearate, 3-5 parts of zinc oxide, 0.5-3 parts of dicumyl peroxide and 1-3 parts of antioxidant; the composite wear-resistant agent is a modified white corundum/graphene oxide composite material.
Further, the ethylene-vinyl acetate copolymer contains 26wt% of VA, the grafting rate of the maleic anhydride grafted EVA is 1.2%, the foaming agent is azodicarbonamide, the accelerator is tetramethylthiuram disulfide, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, the mesh number of white corundum in the composite wear-resistant agent is 500 meshes, and graphene oxide is prepared by a Hummers method.
Further, the preparation method of the modified white corundum/graphene oxide composite material comprises the following steps:
1) dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, and slowly adding 3g of KMnO4After 3 hours of reaction, the system was warmed to 98 ℃. Then 40ml of deionized water, 10ml of 5 wt.% H were added in succession2O2Adding hydrogen peroxide until the solution turns golden yellow and no bubbles are generated, and finally adding 20ml of 5% wtHCl solution;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 percent of hexadecyl trimethyl ammonium bromide solution by mass fraction, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain the modified white corundum material.
3) Taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
The preparation method of the high-mechanical-strength wear-resistant EVA composite foam material comprises the following steps:
(1) respectively dissolving the modified white corundum/graphene oxide composite material and the maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain the premix.
(2) Putting the premix prepared in the step (1) into a torque rheometer for mixing, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
(3) placing the mixed material prepared in the step (2) 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;
(4) weighing a certain mass of the sheet prepared in the step (3) according to the volume of the mould, placing the sheet in 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 high-mechanical-strength wear-resistant EVA composite foam material.
The invention has the beneficial effects that:
EVA foam materials have excellent resilience, flexibility, good foaming properties and load-absorbing ability at normal temperature, and thus are widely used as various sole materials. Traditionally, EVA is singly used as a raw material to prepare a foam material, the compatibility of the foam material with an inorganic filler is poor, and the comprehensive performance cannot meet the requirement.
According to the invention, a proper amount of maleic anhydride grafted EVA and POE are introduced into the raw materials, so that the performance of the composite foam material is effectively improved. The ethylene-octene copolymer (POE) has the advantages of narrow molecular chain, good weather resistance, excellent processing performance and the like, and the toughness and elasticity of the composite material can be improved by introducing a proper amount of POE in the EVA foam material molding process. The maleic anhydride grafted EVA introduces a strong polar side group on the molecular main chain of the EVA, so as to improve the compatibility of the polymer main body and the inorganic filler interface and further improve the comprehensive performance of the composite foam material.
The invention adopts modified white corundum/graphene oxide as a reinforcing material of the composite foam, and at present, the invention technology rarely adds white corundum as an abrasion-resistant filler into organic composite foam materials such as EVA and the like. The white corundum has different particle sizes and poor compatibility with EVA polymers. The hexadecyl trimethyl ammonium bromide is used for modifying the white corundum, so that the dispersibility of the white corundum in the EVA composite material is improved, the agglomeration is reduced, the EVA system is more compact as a whole, the mechanical strength is higher, the load resistance is higher, and the wear resistance of the EVA composite material is further improved. Graphene Oxide (GO) is an important derivative of graphene, has the characteristics of small size, large specific surface area, high strength, a sheet structure and the like, is easy to modify, and has a surface rich in oxygen-containing groups such as hydroxyl, carboxyl and the like, so that the graphene oxide and cetyl trimethyl ammonium bromide modified white corundum are organically combined through hydrogen bond adsorption to form a modified white corundum/graphene oxide composite material.
The modified white corundum/graphene oxide and the grafted EVA are premixed by a solution method, and then are melted, blended and foamed with EVA and the like, so that the compatibility of the modified white corundum/graphene oxide and the EVA is better than that of the modified white corundum/graphene oxide and the EVA which are directly and mechanically blended in a mixing roll. This is beneficial to improving the mechanical property of the composite foam material matrix. Meanwhile, due to the introduction of the rosin resin, the system viscosity of the composite foam material is improved, the hysteresis resistance is increased, the friction coefficient of the composite foam material is increased, and a certain anti-slip property is maintained while the wear resistance of the EVA composite foam material is enhanced.
Compared with the traditional foam material, the wear-resistant EVA composite foam material with high mechanical strength prepared by the invention has the advantages that the wear resistance of the material is enhanced, the better mechanical property is provided, the application range of the foam material is expanded, and a new thought is provided for the functional composite foam material.
Drawings
FIG. 1 is an SEM image of the cross-sectional morphology of the high-mechanical-strength wear-resistant EVA composite foam prepared in example 4;
FIG. 2 is an SEM image of the section morphology of the EVA composite foam prepared 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
A high-mechanical-strength wear-resistant EVA composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 5 parts of rosin resin, 2.5 parts of composite wear-resistant agent, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, slowly adding 3g of KMnO4, reacting for 3 hours, and heating the system to 98 ℃. Then, sequentially adding 40ml of deionized water and 10ml of 5wt% H2O2 hydrogen peroxide until the solution turns golden yellow and no bubbles are generated, and finally adding 20ml of 5% wtHCl solution;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 percent of hexadecyl trimethyl ammonium bromide solution by mass fraction, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain the modified white corundum material.
3) Taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
4) Respectively dissolving the modified white corundum/graphene oxide composite material and the maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain the premix.
5) Mixing the premix prepared in the step 4) in a torque rheometer, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
6) placing the mixed material prepared in the step 5) 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;
7) weighing a certain mass of the sheet prepared in the step 6) according to the volume of the mould, placing the sheet in a preheated mould cavity of a plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the high-mechanical-strength wear-resistant EVA composite foam material.
Example 2
A high-mechanical-strength wear-resistant EVA composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 5 parts of rosin resin, 5 parts of composite wear-resistant agent, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, slowly adding 3g of KMnO4, reacting for 3 hours, and heating the system to 98 ℃. Then, sequentially adding 40ml of deionized water and 10ml of 5wt% H2O2 hydrogen peroxide until the solution turns golden yellow and no bubbles are generated, and finally adding 20ml of 5% wtHCl solution;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 percent of hexadecyl trimethyl ammonium bromide solution by mass fraction, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain the modified white corundum material.
3) Taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
4) Respectively dissolving the modified white corundum/graphene oxide composite material and the maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain the premix.
5) Mixing the premix prepared in the step 4) in a torque rheometer, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
6) placing the mixed material prepared in the step 5) 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;
7) weighing a certain mass of the sheet prepared in the step 6) according to the volume of the mould, placing the sheet in a preheated mould cavity of a plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the high-mechanical-strength wear-resistant EVA composite foam material.
Example 3
A high-mechanical-strength wear-resistant EVA composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 5 parts of rosin resin, 7.5 parts of composite wear-resistant agent, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, slowly adding 3g of KMnO4, reacting for 3 hours, and heating the system to 98 ℃. Then, sequentially adding 40ml of deionized water and 10ml of 5wt% H2O2 hydrogen peroxide until the solution turns golden yellow and no bubbles are generated, and finally adding 20ml of 5% wtHCl solution;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 percent of hexadecyl trimethyl ammonium bromide solution by mass fraction, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain the modified white corundum material.
3) Taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
4) Respectively dissolving the modified white corundum/graphene oxide composite material and the maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain the premix.
5) Mixing the premix prepared in the step 4) in a torque rheometer, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
6) placing the mixed material prepared in the step 5) 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;
7) weighing a certain mass of the sheet prepared in the step 6) according to the volume of the mould, placing the sheet in a preheated mould cavity of a plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the high-mechanical-strength wear-resistant EVA composite foam material.
Example 4
A high-mechanical-strength wear-resistant EVA composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 5 parts of rosin resin, 10 parts of composite wear-resistant agent, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, slowly adding 3g of KMnO4, reacting for 3 hours, and heating the system to 98 ℃. Then, sequentially adding 40ml of deionized water and 10ml of 5wt% H2O2 hydrogen peroxide until the solution turns golden yellow and no bubbles are generated, and finally adding 20ml of 5% wtHCl solution;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 percent of hexadecyl trimethyl ammonium bromide solution by mass fraction, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain the modified white corundum material.
3) Taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
4) Respectively dissolving the modified white corundum/graphene oxide composite material and the maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain the premix.
5) Mixing the premix prepared in the step 4) in a torque rheometer, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
6) placing the mixed material prepared in the step 5) 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;
7) weighing a certain mass of the sheet prepared in the step 6) according to the volume of the mould, placing the sheet in a preheated mould cavity of a plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the high-mechanical-strength wear-resistant EVA composite foam material.
Comparative example 1
A composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Mixing ethylene-vinyl acetate copolymer in a torque rheometer, then sequentially adding maleic anhydride grafted EVA, ethylene-octene copolymer, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, a foaming agent and the like, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 20min, 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 plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the EVA foam composite material.
Comparative example 2
A composite foam material comprises the following raw materials in parts by weight: 75 parts of ethylene-vinyl acetate copolymer, 10 parts of maleic anhydride grafted EVA, 5 parts of ethylene-octene copolymer, 5 parts of rosin resin, 8.3 parts of white corundum, 1.7 parts of graphene oxide, 2 parts of naphthenic oil, 3 parts of foaming agent AC, 1 part of accelerator tetramethyl thiuram disulfide, 1 part of stearic acid, 0.5 part of zinc stearate, 5 parts of zinc oxide, 1.5 parts of dicumyl peroxide and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
1) Putting an ethylene-vinyl acetate copolymer into a torque rheometer for mixing, then sequentially adding maleic anhydride grafted EVA, an ethylene-octene copolymer, rosin resin, white corundum, graphene oxide, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant, a foaming agent and the like, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
2) placing the mixture prepared in the step 1) for 24 hours, then placing the mixture into an open mill for mixing for 20min, 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 plate vulcanizing machine, and carrying out mould pressing foaming for 10min at the temperature of 180 ℃ under the pressure of 15MPa to obtain the EVA foam composite material.
The EVA foam composites obtained from examples 1-4 and comparative examples 1 and 2 were tested for comparative performance and the results are shown in Table 1.
Table 1 comparative testing of properties
In the invention, examples 1 to 4 are respectively a blank comparative example in which the addition amount of the composite wear-resisting agent is 2.5, 5, 7.5 and 10 parts in sequence, comparative example 1 is a blank comparative example in which a functional filler is not added, and comparative example 2 is a comparative example in which a filler with the same proportion is directly and mechanically mixed with EVA. As is obvious from the data in Table 1, the tensile strength, DIN abrasion and other properties of the comparative example 2 are improved to a certain extent compared with those of the comparative example 1 of the blank control group, but the tensile strength, DIN abrasion and other properties are far lower than those of the examples, namely the EVA composite foam material prepared by the invention has more excellent mechanical strength and abrasion resistance.
Example 4 the cross-sectional morphology of the high mechanical strength wear-resistant EVA composite foam material with 10 parts of modified white corundum/graphene oxide added is shown in fig. 1; comparative example 2 the section morphology of the EVA composite foam material added with 8.3 parts of unmodified white corundum and 1.7 parts of graphene oxide is shown in FIG. 2. The example was to mix the filler with the grafted EVA beforehand using a solution process, while the comparative example 2 was to blend the filler directly with EVA or the like mechanically. The result shows that many exposed inorganic additive phase particles on the section can be clearly seen in fig. 2, the section in fig. 1 is smoother than the section in fig. 2, and the added modified filler is better wrapped and dispersed in the polymer matrix, i.e. the modified white corundum/graphene oxide has better compatibility than before modification, which is beneficial to improving the mechanical property and wear resistance of the EVA composite foam material.
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 (4)
1. The high-mechanical-strength wear-resistant EVA composite foam material is characterized in that: the raw materials comprise the following components in parts by weight: 65-75 parts of ethylene-vinyl acetate copolymer, 10-20 parts of maleic anhydride grafted EVA (ethylene-vinyl acetate), 5-10 parts of ethylene-octene copolymer, 5-10 parts of rosin resin, 2-10 parts of composite wear-resistant agent, 2-4 parts of naphthenic oil, 3-5 parts of foaming agent AC, 1-2 parts of accelerator, 0.5-2 parts of stearic acid, 0.5-1.5 parts of zinc stearate, 3-5 parts of zinc oxide, 0.5-3 parts of dicumyl peroxide and 1-3 parts of antioxidant; the composite wear-resistant agent is a modified white corundum/graphene oxide composite material.
2. The high mechanical strength abrasion resistant EVA syntactic foam according to claim 1, wherein: the ethylene-vinyl acetate copolymer contains 26wt% of VA, the grafting rate of maleic anhydride grafted EVA is 1.2%, the foaming agent is azodicarbonamide, the accelerator is tetramethyl thiuram disulfide, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, the mesh number of white corundum in the composite wear-resistant agent is 500 meshes, and graphene oxide is prepared by a Hummers method.
3. The high mechanical strength abrasion resistant EVA syntactic foam according to claim 1, wherein: the preparation method of the composite wear-resistant agent comprises the following steps:
1) dissolving 1g of expanded graphite in 23ml of concentrated sulfuric acid, keeping the uniform magnetic stirring state, and slowly adding 3g of KMnO4After reacting for 3 hours, the system was heated to 98 ℃ and then 40ml of deionized water and 10ml of 5wt% H were sequentially added2O2Hydrogen peroxide until the solution turned golden yellow and no bubbles were produced, and finally 20ml of 5% wtHCl solution was added; centrifuging and washing the suspension to be neutral, and freeze-drying to obtain graphene oxide;
2) taking pre-dried white corundum, mixing 1 g: adding 10ml of the mixture into 1 mass percent of hexadecyl trimethyl ammonium bromide solution, stirring and reacting for 5 hours at room temperature, and washing and drying to obtain a modified white corundum material;
3) taking the graphene oxide prepared in the step 1) and the modified white corundum prepared in the step 2) according to the weight ratio of 1: 5, respectively dissolving the components in absolute ethyl alcohol according to a mass ratio, magnetically stirring the mixture for 6 hours at the temperature of 60 ℃, and washing and drying the mixture to obtain the modified white corundum/graphene oxide composite material.
4. A method for preparing a high mechanical strength abrasion resistant EVA syntactic foam according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) respectively dissolving the modified white corundum/graphene oxide composite material and maleic anhydride grafted EVA in an N, N-dimethylformamide solution, then adding the modified white corundum/graphene oxide solution into the maleic anhydride grafted EVA solution, fully and uniformly stirring, putting the mixed solution into a vacuum drying oven, and standing for 12 hours at 80 ℃ to obtain a premix;
(3) putting the premix prepared in the step (1) into a torque rheometer for mixing, then sequentially adding an ethylene-vinyl acetate copolymer, an ethylene-octene copolymer, rosin resin, naphthenic oil, stearic acid, zinc stearate, zinc oxide, an accelerator, dicumyl peroxide, an antioxidant and a foaming agent, and mixing for 15min at 105 ℃ and 40rpm to obtain a mixed material;
(4) placing the mixed material prepared in the step (3) 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;
(5) weighing a certain mass of the sheet prepared in the step (3) according to the volume of the mould, placing the sheet in 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 high-mechanical-strength wear-resistant EVA composite foam material.
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