CN111978609A - Wear-resistant sole material and preparation method thereof - Google Patents
Wear-resistant sole material and preparation method thereof Download PDFInfo
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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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
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention provides a wear-resistant sole material which is prepared from the following raw materials in parts by weight: 10-60 parts of wear-resistant thermoplastic elastomer, 40-90 parts of nitrile rubber, 0.5-5 parts of zinc stearate, 0.1-2 parts of antioxidant 1098, 0.1-2 parts of white mineral oil and 1-10 parts of talcum powder. The wear-resistant sole material prepared by the invention has good mechanical property and wear resistance.
Description
Technical Field
The invention relates to the technical field of shoe material manufacturing, in particular to a wear-resistant sole material and a preparation method thereof.
Background
The shoes as necessary daily necessities have the same main structure as a shoe upper, a shoe body inner, a middle sole and an outer sole although the variety is various. The quality of a pair of shoes mainly depends on soles, each sole consists of a midsole and an outsole, and the soles prepared by traditional polymer materials such as animal leather, natural rubber, polyvinyl chloride and the like have the defects of heaviness, poor air permeability, poor comfort and the like. With the increasing demand of people for wearing shoes, the shoes which pursue special functions such as light weight, wear resistance, fashion, skid resistance and wear resistance become the hot demand of people.
The traditional shoe material is difficult to meet the requirements of people on functional shoe materials, and the preparation of novel sole materials with higher resilience, high strength, light weight, wear resistance and lower compression deformation is a future development trend. How to realize the performances of light weight, wear resistance, comfort and the like of shoe materials and ensure that the resilience, the mechanical property and the like of the shoe materials are not influenced is the problem to be continuously solved for modifying the shoe materials.
Disclosure of Invention
The invention aims to provide a wear-resistant sole material and a preparation method thereof.
The technical scheme of the invention is realized as follows:
the invention provides a wear-resistant sole material which is prepared from the following raw materials: wear-resistant thermoplastic elastomer, nitrile rubber, zinc stearate, an antioxidant 1098, white mineral oil and talcum powder.
Preferably, the wear-resistant sole material is prepared from the following raw materials in parts by weight: 10-60 parts of wear-resistant thermoplastic elastomer, 40-90 parts of nitrile rubber, 0.5-5 parts of zinc stearate, 0.1-2 parts of antioxidant 1098, 0.1-2 parts of white mineral oil and 1-10 parts of talcum powder.
Preferably, the wear-resistant sole material is prepared by the following method:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 1-10min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and continuing stirring for 1-10 min; then sending the mixture into an internal mixer for banburying for 5-25min at the temperature of 180-; and then sending the mixture into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing the mixture into a vulcanizing machine for vulcanization for 10-30min, wherein the vulcanization temperature is 160-200 ℃, and the vulcanization pressure is 15-25 MPa.
The preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 50-120 parts by weight of polyether to 90-120 ℃, dehydrating for 1-2 hours, adding the dehydrated polyether into a reactor which is added with 70-150 parts by weight of isocyanate and has a temperature of 60-80 ℃, starting stirring, and reacting for 1-3 hours to obtain a polyether type prepolymer;
s2, dropwise adding a ferric chloride solution into a sodium hydroxide solution, standing until a solid is separated out, carrying out suction filtration, removing a filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
the chemical reaction equation is as follows:
3NaOH+FeCl3＝Fe(OH)3(colloid) +3NaCl
S3, adding 10-20 parts by weight of inorganic nanoparticles into 50-100 parts by weight of an ethanol solution of a silane coupling agent, wherein the mass fraction of the silane coupling agent is 1.5-2.5%, heating to 50-70 ℃, reacting for 0.5-2h, adding 15-25 parts by weight of the solid prepared in the step S2, heating to 75-85 ℃, continuing to react for 1-2h, and filtering to obtain a solid for later use;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 30-40min to obtain particles;
s5, respectively adding 30-60 parts of caprolactam and 18-36 parts of hexamethylene adipamide into A, B two kettles by weight, heating to melt and raise the temperature to 140 ℃, performing vacuum dehydration for 10-20min, adding 10-30 parts of NaOH and all the particles prepared in the step S4 into the kettle A, adding the prepolymer prepared in the step S1 into the kettle B, performing vacuum dehydration for 20-40min, mixing the materials in the two kettles, stirring for 2-3S, and performing open milling to obtain a mixed material, wherein the open mill temperature is 150-180 ℃, and the open milling time is 20-50 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 0.5-5mm to obtain the wear-resistant thermoplastic elastomer.
As a further improvement of the invention, the preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 50-120 parts by weight of polyether to 90-120 ℃, dehydrating for 1-2 hours, adding the dehydrated polyether into a reactor which is added with 70-150 parts by weight of isocyanate and has a temperature of 60-80 ℃, starting stirring, and reacting for 1-3 hours to obtain a polyether type prepolymer;
s2, dropwise adding a ferric chloride solution into a sodium hydroxide solution, standing until a solid is separated out, carrying out suction filtration, removing a filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 10-20 parts by weight of inorganic nanoparticles into 50-100 parts by weight of an ethanol solution of a silane coupling agent, heating to 50-70 ℃ to react for 0.5-2h, adding 15-25 parts by weight of the solid prepared in the step S2, heating to 75-85 ℃, continuing to react for 1-2h, filtering, and keeping the solid for use;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 30-40min to obtain particles;
s5, respectively adding 30-60 parts of caprolactam and 18-36 parts of hexamethylene adipamide into A, B two kettles by weight, heating, melting and heating to 140 ℃, performing vacuum dehydration for 10-20min, adding 5-10 parts of sulfur, 5-20 parts of NaOH and all the particles prepared in the step S4 into the kettle A, adding all the prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 20-40min, mixing the materials in the two kettles, stirring for 2-3S, performing open milling to obtain a mixed material, wherein the open mill temperature is 180 ℃ for 150 and the open milling time is 20-50 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 0.5-5mm to obtain the wear-resistant thermoplastic elastomer.
As a further improvement of the invention, the preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 50-120 parts by weight of polyether to 90-120 ℃, dehydrating for 1-2 hours, adding the dehydrated polyether into a reactor which is added with 70-150 parts by weight of isocyanate and has a temperature of 60-80 ℃, starting stirring, and reacting for 1-3 hours to obtain a polyether type prepolymer;
s2, dropwise adding a ferric chloride solution into a sodium hydroxide solution, standing until a solid is separated out, carrying out suction filtration, removing a filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 10-20 parts by weight of inorganic nanoparticles into 50-100 parts by weight of an ethanol solution of a silane coupling agent, heating to 50-70 ℃ to react for 0.5-2h, adding 15-25 parts by weight of the solid prepared in the step S2, heating to 75-85 ℃, continuing to react for 1-2h, filtering, and keeping the solid for use;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 30-40min to obtain particles;
s5, respectively adding 30-60 parts of caprolactam and 18-36 parts of hexamethylene adipamide into A, B two kettles by weight, heating, melting and heating to 140 ℃, performing vacuum dehydration for 10-20min, adding 4-5 parts of dicumyl peroxide, 1-5 parts of methacrylate, 5-20 parts of NaOH and particles prepared in the step S4 into the kettle A, adding prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 20-40min, mixing the materials in the two kettles, stirring for 2-3S, performing open milling to obtain a mixed material, wherein the open mill temperature is 150-180 ℃, and the open milling time is 20-50 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 0.5-5mm to obtain the wear-resistant thermoplastic elastomer.
Preferably, in step S1, the polyether is selected from one or more of polytetrahydrofuran ether, polyethylene glycol ether, polypropylene glycol ether, polybutylene glycol ether and polypropylene oxide ether; the isocyanate is selected from one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, 4' -triphenylmethane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate. Further preferably, the polyether in step S1 is polytetrahydrofuran ether; the isocyanate is toluene diisocyanate.
Preferably, the mass concentration of the sodium hydroxide solution in the step S2 is 1-2 mol/L; the mass concentration of the ferric chloride solution is 0.5-2 mol/L.
Preferably, in step S3, the inorganic nanoparticles are selected from one or more of nano calcium carbonate, nano zinc oxide, nano silver, nano copper, nano barium sulfate and nano montmorillonite; further, the inorganic nano particles are a mixture of nano calcium carbonate and nano zinc oxide according to the mass ratio of (1-5) to 1; the silane coupling agent is selected from one or a mixture of KH550, KH560 and KH 570.
The invention has the following beneficial effects: the inorganic nano particles are coated with ferric hydroxide after surface modification to form microspheres, the microspheres are added into a polymerization reaction of a polyamide matrix, and can be uniformly and respectively formed in a polyamide elastomer to form core-shell colloidal particles, cavitation of the core-shell colloidal particles and shear yield of a matrix polymer can occur, namely, in an impact process, the core-shell colloidal particles are subjected to cavitation action firstly to trigger matrix shear yield deformation, and the slippage and plastic flow of molecular chains are promoted by the ball effect of a core-shell coating structure of the elastomer coated nano inorganic particles, so that the breaking strain is increased, and the impact strength is improved. When the thermoplastic elastomer bears load, the 'ball' can be smoothly transmitted to the plastic matrix, in addition, the iron hydroxide colloid can avoid causing fiber fatigue damage when the 'ball' bears load as the cotton-shaped flocculent protective layer, the iron hydroxide and other organic components generate complex reaction, and the generation of uncontrollable and non-uniformly distributed brittle interaction is avoided, so that the impact strength and the toughness of the composite material are greatly improved.
Dicumyl peroxide and methacrylate are mixed and added into the system to have a synergistic effect. The network formed by vulcanizing agent dicumyl peroxide often has good aging resistance, the active auxiliary agent methacrylate is added, homopolymerization can be carried out, effective cross-linking bonds are generated through free radical addition reaction, the cross-linking density of the network is improved, the composition of the cross-linking bonds is changed, the network is enhanced by grafting among polymer chains, an interpenetrating network of the homopolymerization active auxiliary agent is formed, and a filler-shaped area with high thermosetting active auxiliary agent modulus is formed, so that the cross-linking density is higher, and the network has better mechanical property and wear resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Introduction of some raw materials in this application:
nitrile rubber, JSRN220S nitrile rubber, available from shanghai judao chemical industry.
White mineral oil, no: HBS-L278, CAS number: 8042-47-5, available from waie technologies, inc.
Talc, CAS No.: 14807-96-6; particle size 800 mesh, purchased from Shanghai Tantake Technique, Inc.
Nano zinc oxide, CAS No.: 1314-13-2; the particle size is 20nm, and the particle size is purchased from Nanjing Xiancheng nanometer material science and technology Limited.
Nano calcium carbonate, CAS number: 471-34-1; particle size 40nm, available from Shanghai Dairy Fine Chemicals, Inc.
Example 1
The wear-resistant sole material is prepared from the following raw materials in parts by weight: 40 parts of wear-resistant thermoplastic elastomer, 52 parts of nitrile rubber, 1 part of zinc stearate, 0.5 part of antioxidant 1098, 0.5 part of white mineral oil and 6 parts of talcum powder.
The wear-resistant sole material is prepared by the following method:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 4min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and stirring for 6 min; then sending the mixture into an internal mixer for internal mixing for 10min at the temperature of 195 ℃; and then sending into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing into a vulcanizing machine for vulcanization treatment for 20min, wherein the vulcanization temperature is 180 ℃ and the vulcanization pressure is 20 MPa.
The preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 70g of polytetrahydrofuran ether to 100 ℃, dehydrating for 1.5h, then adding the dehydrated polytetrahydrofuran ether into a reactor which is added with 100g of toluene diisocyanate and has a temperature of 70 ℃, starting stirring at a rotating speed of 500r/min, and reacting for 2h to obtain a polyether type prepolymer;
s2, dropwise adding 1mol/L ferric chloride solution into 1.5mol/L sodium hydroxide solution, wherein the mass ratio of sodium hydroxide to ferric chloride is 3:1, standing until a solid is precipitated, performing suction filtration, removing filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 15g of inorganic nanoparticles into 70g of ethanol solution of silane coupling agent KH550, heating to 60 ℃, reacting for 1h, adding 20g of solid prepared in the step S2, heating to 80 ℃, continuing to react for 1.5h, and filtering to obtain solid for later use, wherein the mass fraction of the silane coupling agent KH550 in the ethanol solution of silane coupling agent KH550 is 2%; the inorganic nano particles are nano zinc oxide;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 35min to obtain particles;
s5, respectively adding 45g of caprolactam and 24g of hexamethylene adipamide into A, B two kettles, heating, melting and heating to 140 ℃, performing vacuum dehydration for 15min, adding 20g of NaOH and all the particles prepared in the step S4 into the kettle A, adding all the polyether type prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 30min, mixing the materials in the two kettles, stirring for 3S, performing open milling to obtain a mixed material, wherein the temperature of an open mill is 170 ℃, and the open milling time is 25 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 2mm to obtain the wear-resistant thermoplastic elastomer.
Comparative example 1
Compared with example 1, no silane coupling agent was added, and other conditions were not changed.
The wear-resistant sole material is prepared from the following raw materials in parts by weight: 40 parts of wear-resistant thermoplastic elastomer, 52 parts of nitrile rubber, 1 part of zinc stearate, 0.5 part of antioxidant 1098, 0.5 part of white mineral oil and 6 parts of talcum powder.
The wear-resistant sole material is prepared by the following method:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 4min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and stirring for 6 min; then sending the mixture into an internal mixer for internal mixing for 10min at the temperature of 195 ℃; and then sending into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing into a vulcanizing machine for vulcanization treatment for 20min, wherein the vulcanization temperature is 180 ℃ and the vulcanization pressure is 20 MPa.
The preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 70g of polytetrahydrofuran ether to 100 ℃, dehydrating for 1.5h, then adding the dehydrated polytetrahydrofuran ether into a reactor which is added with 100g of toluene diisocyanate and has a temperature of 70 ℃, starting stirring at a rotating speed of 500r/min, and reacting for 2h to obtain a polyether type prepolymer;
s2, dropwise adding 1mol/L ferric chloride solution into 1.5mol/L sodium hydroxide solution, wherein the mass ratio of sodium hydroxide to ferric chloride is 3:1, standing until a solid is precipitated, performing suction filtration, removing filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 15g of inorganic nanoparticles into 70g of absolute ethyl alcohol, heating to 60 ℃, reacting for 1 hour, adding 20g of the solid prepared in the step S2, heating to 80 ℃, continuing to react for 1.5 hours, and filtering to obtain a solid for later use; the inorganic nano particles are nano zinc oxide;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 35min to obtain particles;
s5, respectively adding 45g of caprolactam and 24g of hexamethylene adipamide into A, B two kettles, heating, melting and heating to 140 ℃, performing vacuum dehydration for 15min, adding 20g of NaOH and all the particles prepared in the step S4 into the kettle A, adding all the polyether type prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 30min, mixing the materials in the two kettles, stirring for 3S, performing open milling to obtain a mixed material, wherein the temperature of an open mill is 170 ℃, and the open milling time is 25 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 2mm to obtain the wear-resistant thermoplastic elastomer.
Comparative example 2
Compared with example 5, no iron hydroxide colloid was added, and other conditions were not changed.
The wear-resistant sole material is composed of the following raw materials in parts by weight: 40 parts of wear-resistant thermoplastic elastomer, 52 parts of nitrile rubber, 1 part of zinc stearate, 0.5 part of antioxidant 1098, 0.5 part of white mineral oil and 6 parts of talcum powder.
The wear-resistant sole material is prepared by the following method:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 4min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and stirring for 6 min; then sending the mixture into an internal mixer for internal mixing for 10min at the temperature of 195 ℃; and then sending into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing into a vulcanizing machine for vulcanization treatment for 20min, wherein the vulcanization temperature is 180 ℃ and the vulcanization pressure is 20 MPa.
The preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 70g of polytetrahydrofuran ether to 100 ℃, dehydrating for 1.5h, then adding the dehydrated polytetrahydrofuran ether into a reactor which is added with 100g of toluene diisocyanate and has a temperature of 70 ℃, starting stirring at a rotating speed of 500r/min, and reacting for 2h to obtain a polyether type prepolymer;
s2, adding 15g of inorganic nanoparticles into 70g of an ethanol solution of a silane coupling agent KH550, heating to 60 ℃, reacting for 1h, heating to 80 ℃, continuing to react for 1.5h, and filtering to obtain a solid for later use, wherein the mass fraction of the silane coupling agent KH550 in the ethanol solution of the silane coupling agent KH550 is 2%; the inorganic nano particles are nano zinc oxide;
s3, adding the solid prepared in the step S2 into a ball mill for ball milling for 35min to obtain particles;
s4, respectively adding 45g of caprolactam and 24g of hexamethylene adipamide into A, B two kettles, heating, melting and heating to 140 ℃, performing vacuum dehydration for 15min, adding 20g of NaOH and all the particles prepared in the step S3 into the kettle A, adding all the polyether type prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 30min, mixing the materials in the two kettles, stirring for 3S, performing open milling to obtain a mixed material, wherein the temperature of an open mill is 170 ℃, and the open milling time is 25 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 2mm to obtain the wear-resistant thermoplastic elastomer.
Example 2
Compared with the example 1, the inorganic nano particles are nano calcium carbonate, and other conditions are not changed.
Example 3
Compared with the embodiment 1, the inorganic nano particles are a mixture of nano calcium carbonate and nano zinc oxide, the mass ratio is 3:1, and other conditions are not changed.
Example 4
The wear-resistant sole material is prepared from the following raw materials in parts by weight: 40 parts of wear-resistant thermoplastic elastomer, 52 parts of nitrile rubber, 1 part of zinc stearate, 0.5 part of antioxidant 1098, 0.5 part of white mineral oil and 6 parts of talcum powder.
The wear-resistant sole material is prepared by the following method:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 4min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and stirring for 6 min; then sending the mixture into an internal mixer for internal mixing for 10min at the temperature of 195 ℃; and then sending into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing into a vulcanizing machine for vulcanization treatment for 20min, wherein the vulcanization temperature is 180 ℃ and the vulcanization pressure is 20 MPa.
The preparation method of the wear-resistant thermoplastic elastomer comprises the following steps:
s1, heating 70g of polytetrahydrofuran ether to 100 ℃, dehydrating for 1.5h, then adding the dehydrated polytetrahydrofuran ether into a reactor which is added with 100g of toluene diisocyanate and has a temperature of 70 ℃, starting stirring at a rotating speed of 500r/min, and reacting for 2h to obtain a polyether type prepolymer;
s2, dropwise adding 1mol/L ferric chloride solution into 1.5mol/L sodium hydroxide solution, wherein the mass ratio of sodium hydroxide to ferric chloride is 3:1, standing until a solid is precipitated, performing suction filtration, removing filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 15g of inorganic nanoparticles (the inorganic nanoparticles are a mixture of nano calcium carbonate and nano zinc oxide, the mass ratio is 3:1) into 70g of an ethanol solution of a silane coupling agent KH550, heating to 60 ℃, reacting for 1h, adding 20g of the solid prepared in the step S2, heating to 80 ℃, continuing to react for 1.5h, filtering, and keeping the solid for use;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 35min to obtain particles;
s5, respectively adding 45g of caprolactam and 24g of hexamethylene adipamide into A, B two kettles, heating, melting, heating to 140 ℃, performing vacuum dehydration for 15min, adding 5g of sulfur, 15g of NaOH and all the particles prepared in the step S4 into the kettle A, adding all the polyether type prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 30min, mixing the materials in the two kettles, stirring for 3S, performing open milling to obtain a mixture, wherein the temperature of an open mill is 170 ℃, and the open milling time is 25 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 2mm to obtain the wear-resistant thermoplastic elastomer.
Example 5
Compared with example 4, 5g of sulphur was replaced by 4g of dicumyl peroxide and 1g of methacrylate, all other conditions being unchanged.
Comparative example 3
In comparison with example 4, 5g of sulphur was replaced by 5g of dicumyl peroxide, the other conditions being unchanged.
Comparative example 4
In comparison with example 4, 5g of sulphur was replaced by 5g of methacrylate, the other conditions being unchanged.
Test example 1
And (3) testing mechanical properties: the wear-resistant sole materials prepared in the examples and the comparative examples of the invention were subjected to mechanical property detection, and 5 groups were paralleled and averaged.
1. The tensile properties were measured according to GB/T528-2009 Standard using a type 1 dumbbell specimen specified in the Standard at a tensile rate of 500. + -. 50 mm/min.
2. The impact strength test was carried out according to HG/T3845-2008 standard.
3. The bending performance test is carried out according to the HG/T3844-2008 standard.
TABLE 1
As can be seen from comparison of examples 1-3, the invention adopts the compounding of nano calcium carbonate and nano zinc oxide, and then carries out surface treatment to form the core-shell structure copolymer, thus improving the dispersibility and compatibility of the core-shell structure copolymer, and being not easy to agglomerate in the polymer, thereby improving the mechanical property of the polymer. In the impact process, the core-shell colloidal particles firstly generate cavitation to initiate shearing yield deformation of a matrix, and the 'ball' action of the core-shell coating structure of the elastomer coating nano inorganic particles promotes the slippage and plastic flow of molecular chains, so that the fracture strain is increased, and the impact strength is improved. When the thermoplastic elastomer bears load, the 'ball' can be smoothly transmitted to the plastic matrix, in addition, the iron hydroxide colloid can avoid causing fiber fatigue damage when the 'ball' bears load as the cotton-shaped flocculent protective layer, the iron hydroxide and other organic components generate complex reaction, and the generation of uncontrollable and non-uniformly distributed brittle interaction is avoided, so that the impact strength and the toughness of the material are greatly improved.
Comparing comparative examples 1-2 with example 5, it can be seen that the silane coupling agent can coat colloidal iron hydroxide ions on the surface of inorganic nanoparticles well, the core-shell structure is well formed in the polyamide elastomer matrix, the dispersibility is increased, the mechanical property is improved, the inorganic nano particles are coated by ferric hydroxide after the surface is modified to form microspheres, the microspheres are added into the polymerization reaction of the polyamide matrix, can be uniformly distributed in an elastomer to form core-shell colloidal particles, the cavitation of the core-shell colloidal particles and the shear yield of a matrix polymer can occur, namely, in the impact process, the core-shell colloidal particles firstly generate cavitation to trigger the shearing yield deformation of the matrix, and the 'ball' action of the core-shell coating structure of the elastomer coating nano inorganic particles promotes the slippage and plastic flow of molecular chains, so that the fracture strain is increased, and the impact strength is improved.
Test example 2
And (3) testing the wear resistance: the wear-resistant sole materials prepared in the embodiments and the comparative examples of the invention are subjected to wear resistance detection according to GB/T9867-2008; the spinning samples specified in standard test method B were used. Parallel to 5 groups, average.
TABLE 2 DIN abrasion test
| DIN abrasion mm3 | |
| Example 1 | 98.0 |
| Example 2 | 97.2 |
| Example 3 | 95.5 |
| Example 4 | 91.2 |
| Example 5 | 88.0 |
| Comparative example 3 | 93.7 |
| Comparative example 4 | 95.0 |
Comparing examples 4-5, it can be seen that the invention adopts dicumyl peroxide and methacrylate to replace sulfur as a crosslinking assistant, and under certain temperature and pressure conditions, linear macromolecules are converted into a three-dimensional network structure; the network structure formed by vulcanizing the peroxide has good aging resistance, homopolymerization can be carried out by using the active auxiliary agent methacrylate, effective cross-linking bonds are generated through free radical addition reaction, the cross-linking density of the network is improved, the composition of the cross-linking bonds is changed, the network is enhanced by grafting between polymer chains, an interpenetrating network of the homopolymerization active auxiliary agent is formed, and a filler-shaped area with higher modulus of the thermosetting active auxiliary agent is formed, so that the cross-linking density is higher, and the network structure has better mechanical property and wear resistance.
Comparing comparative examples 3-4 with example 5, it can be seen that the combination of dicumyl peroxide and methacrylate in the system has a synergistic effect. The network formed by vulcanizing agent dicumyl peroxide often has good aging resistance, the active auxiliary agent methacrylate is added, homopolymerization can be carried out, effective cross-linking bonds are generated through free radical addition reaction, the cross-linking density of the network is improved, the composition of the cross-linking bonds is changed, the network is enhanced by grafting among polymer chains, an interpenetrating network of the homopolymerization active auxiliary agent is formed, and a filler-shaped area with high thermosetting active auxiliary agent modulus is formed, so that the cross-linking density is higher, and the network has better mechanical property and wear resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The wear-resistant sole material is characterized by comprising the following raw materials: wear-resistant thermoplastic elastomer, nitrile rubber, zinc stearate, an antioxidant 1098, white mineral oil and talcum powder.
2. The wear-resistant sole material according to claim 1, which is prepared from the following raw materials in parts by weight: 10-60 parts of wear-resistant thermoplastic elastomer, 40-90 parts of nitrile rubber, 0.5-5 parts of zinc stearate, 0.1-2 parts of antioxidant 1098, 0.1-2 parts of white mineral oil and 1-10 parts of talcum powder.
3. The wear resistant sole material according to claim 1, characterized in that the method of preparing the wear resistant thermoplastic elastomer comprises the steps of:
s1, heating 50-120 parts by weight of polyether to 90-120 ℃, dehydrating for 1-2 hours, adding the dehydrated polyether into a reactor which is added with 70-150 parts by weight of isocyanate and has a temperature of 60-80 ℃, starting stirring, and reacting for 1-3 hours to obtain a polyether type prepolymer;
s2, dropwise adding a ferric chloride solution into a sodium hydroxide solution, standing until a solid is separated out, carrying out suction filtration, removing a filtrate, and repeatedly washing the solid with deionized water until the pH value is 7;
s3, adding 10-20 parts by weight of inorganic nanoparticles into 50-100 parts by weight of an ethanol solution of a silane coupling agent, heating to 50-70 ℃ to react for 0.5-2h, adding 15-25 parts by weight of the solid prepared in the step S2, heating to 75-85 ℃, continuing to react for 1-2h, filtering, and keeping the solid for use;
s4, adding the solid prepared in the step S3 into a ball mill for ball milling for 30-40min to obtain particles;
s5, respectively adding 30-60 parts of caprolactam and 18-36 parts of hexamethylene adipamide into A, B two kettles by weight, heating, melting and heating to 140 ℃, performing vacuum dehydration for 10-20min, adding 5-10 parts of sulfur, 5-20 parts of NaOH and all the particles prepared in the step S4 into the kettle A, adding all the prepolymers prepared in the step S1 into the kettle B, performing vacuum dehydration for 20-40min, mixing the materials in the two kettles, stirring for 2-3S, performing open milling to obtain a mixed material, wherein the open mill temperature is 180 ℃ for 150 and the open milling time is 20-50 min; and (3) putting the mixture into a granulator, and granulating into particles with the diameter of 0.5-5mm to obtain the wear-resistant thermoplastic elastomer.
4. The wear-resistant sole material according to claim 3, wherein the inorganic nanoparticles are selected from one or a mixture of several of nano calcium carbonate, nano zinc oxide, nano silver, nano copper, nano barium sulfate and nano montmorillonite; the silane coupling agent is selected from one or a mixture of KH550, KH560 and KH 570.
5. The wear-resistant sole material according to claim 3, characterized in that it is prepared by a method comprising:
adding the wear-resistant thermoplastic elastomer and the nitrile rubber into a mixer according to the formula, stirring for 1-10min, adding the zinc stearate, the antioxidant 1098, the white mineral oil and the talcum powder, and continuing stirring for 1-10 min; then sending the mixture into an internal mixer for banburying for 5-25min at the temperature of 180-; and then sending the mixture into a granulator for extrusion granulation, finally carrying out compression molding by a film pressing molding machine, and then placing the mixture into a vulcanizing machine for vulcanization for 10-30min, wherein the vulcanization temperature is 160-200 ℃, and the vulcanization pressure is 15-25 MPa.
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| CN202010941996.1A CN111978609A (en) | 2020-09-09 | 2020-09-09 | Wear-resistant sole material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457536A (en) * | 2020-11-26 | 2021-03-09 | 莆田市涵江怡丰鞋业有限公司 | Preparation method of anti-skid wear-resistant boots |
| CN113549317A (en) * | 2021-07-28 | 2021-10-26 | 莆田鸿途鞋塑有限公司 | Wear-resistant rubber sole and preparation method thereof |
| CN113956547A (en) * | 2021-11-09 | 2022-01-21 | 湖南弘辉科技有限公司 | Capsule material for marine air spring and preparation method thereof |
| CN114098217A (en) * | 2021-10-29 | 2022-03-01 | 振扬实业(河源)有限公司 | Thermoplastic elastomer shoe body and manufacturing method thereof |
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2020
- 2020-09-09 CN CN202010941996.1A patent/CN111978609A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457536A (en) * | 2020-11-26 | 2021-03-09 | 莆田市涵江怡丰鞋业有限公司 | Preparation method of anti-skid wear-resistant boots |
| CN112457536B (en) * | 2020-11-26 | 2023-03-17 | 莆田市涵江怡丰鞋业有限公司 | Preparation method of anti-skid wear-resistant boots |
| CN113549317A (en) * | 2021-07-28 | 2021-10-26 | 莆田鸿途鞋塑有限公司 | Wear-resistant rubber sole and preparation method thereof |
| CN114098217A (en) * | 2021-10-29 | 2022-03-01 | 振扬实业(河源)有限公司 | Thermoplastic elastomer shoe body and manufacturing method thereof |
| CN113956547A (en) * | 2021-11-09 | 2022-01-21 | 湖南弘辉科技有限公司 | Capsule material for marine air spring and preparation method thereof |
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