CA3043354C - A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams - Google Patents
A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams 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
- C08L9/06—Copolymers with styrene
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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
- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
Provided are a styrene-butadiene rubber based nano composite foaming material with high shrinkage stability and a preparation method therefor. Styrene-butadiene rubber/ethylene-vinyl acetate, white carbon black, zinc oxide and stearic acid are uniformly and fully mixed in an internal mixer; then a foaming agent, a crosslinking agent, sulphur, an accelerant and paraffin are added to the internal mixer, and mixed to obtain a mixture; organic modified montmorillonoid, organic modified attapulgite and the mixture are added together to the internal mixer, and fully and uniformly mixed, the mixture is pressed into a sheet on an open two-roll mixer, and the sheet is put into a vulcanizing machine and subjected to molding-pressing and cross-linked foaming, and the sheet is discharged and cooled to obtain a styrene-butadiene rubber based foamed sole material. The composite foamed sole material is prepared by blending a binary compounding system of SBR and EVA with inorganic nano particles, and the composite foamed sole material has a better shrinkage ratio, after-shrinkage ratio, density, hardness and compression set resistance.
Description
A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams The invention relates to the preparation of polymer foam, involving a method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
Background technology Polymer foams is a kind of gas/solid two-phase composite consisting of polymer matrix and gas molecules. Bubbles can dramatically change the morphology, structure and properties of polymers, giving them unique properties such as lightweight, elasticity, flexibility, thermal insulation, insulation, shock and sound insulation. Rubber foams is also known as rubber sponge. It takes rubber as the matrix and adds foaming agent, crosslinlcing agent and other additives to prepare foam rubber material with a large number of pores.
The processing property of styrene butadiene rubber (SBR) and the usability of its products are close to the natural rubber. It has some properties such as wear-resistant, heat-resistant, aging resistance and vulcanization speed are better than that of natural rubber. It can be used together with natural rubber or a variety of synthetic rubber and it is the most largely quantity used in general synthetic rubber. Compared with Ethylene-Propylene-Diene Monomer, Polyisoprene Rubber, Natural Rubber and other general synthetic rubber, it has great market advantages Date Recue/Date Received 2022-05-30 in variety, quality and price.
SBR foams has low density, high specific strength, excellent flexibility, shock resistance and superb wear resistance due to the existence of gas phase. At present, it has been used in diving suits, thermal insulation material and other fields. Its application in sole material is very few.
Because polymer foams used in sole is required especially in low shrinkage, low compression, low density; moderate hardness and high stability.
However, SBR foams showed a high shrinkage (about 10%), poor stability (post shrinkage is up to 50%) and low yield.
Summary One purpose of the invention is to provide a method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams. The SBR foams showed low shrinkage, low density and low compression.
In one aspect, there is provide a method for the preparation of high shrinkage stability styrene butadiene rubber-based nanocomposite foams comprising the following steps:
(1) mixing 100 parts of styrene-butadiene rubber and ethylene-vinyl acetate, 20-30 parts of white carbon black, 5.0-10.0 parts of zinc oxide and 1.0-5.0 parts of stearic acid by weight in a mixer;
Background technology Polymer foams is a kind of gas/solid two-phase composite consisting of polymer matrix and gas molecules. Bubbles can dramatically change the morphology, structure and properties of polymers, giving them unique properties such as lightweight, elasticity, flexibility, thermal insulation, insulation, shock and sound insulation. Rubber foams is also known as rubber sponge. It takes rubber as the matrix and adds foaming agent, crosslinlcing agent and other additives to prepare foam rubber material with a large number of pores.
The processing property of styrene butadiene rubber (SBR) and the usability of its products are close to the natural rubber. It has some properties such as wear-resistant, heat-resistant, aging resistance and vulcanization speed are better than that of natural rubber. It can be used together with natural rubber or a variety of synthetic rubber and it is the most largely quantity used in general synthetic rubber. Compared with Ethylene-Propylene-Diene Monomer, Polyisoprene Rubber, Natural Rubber and other general synthetic rubber, it has great market advantages Date Recue/Date Received 2022-05-30 in variety, quality and price.
SBR foams has low density, high specific strength, excellent flexibility, shock resistance and superb wear resistance due to the existence of gas phase. At present, it has been used in diving suits, thermal insulation material and other fields. Its application in sole material is very few.
Because polymer foams used in sole is required especially in low shrinkage, low compression, low density; moderate hardness and high stability.
However, SBR foams showed a high shrinkage (about 10%), poor stability (post shrinkage is up to 50%) and low yield.
Summary One purpose of the invention is to provide a method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams. The SBR foams showed low shrinkage, low density and low compression.
In one aspect, there is provide a method for the preparation of high shrinkage stability styrene butadiene rubber-based nanocomposite foams comprising the following steps:
(1) mixing 100 parts of styrene-butadiene rubber and ethylene-vinyl acetate, 20-30 parts of white carbon black, 5.0-10.0 parts of zinc oxide and 1.0-5.0 parts of stearic acid by weight in a mixer;
(2) adding 0.5-5.0 parts of azodicarbonamide, 0.1-2.0 parts of dicumyl peroxide, 0.5-5.0 parts of sulfur and an accelerator, and 0.5-5.5 Date Recue/Date Received 2022-05-30 parts paraffin wax by weight into the mixer to obtain a mixture;
(3) adding 1.0 parts by weight of organic modified montmorillonite and organic modified attapulgite with ratio of 1:10 ¨ 10:1 into the mixture in the mixer, mixing;
(4) pressing the mixture into a sheet with a thickness of 1-5 mm on an open two-roll mixer;
(5) preheating an embedded mold in a vulcanizer to 190-200 C, evenly spraying a polysiloxane water-based emulsion release agent, and drying by evaporation;
(6) putting the sheet into the vulcanizer, cross-linking and foam molding the sheet, and cooling to 25 C to obtain the high shrinkage stability styrene-butadiene rubber-based nanocomposite foams; wherein in step (1), a molar ratio of the styrene-butadiene rubber to the ethylene-vinyl acetate is 1:10 ¨ 5:5;
a styrene monomer unit in the styrene-butadiene rubber is 22%-25%, and a vinyl acetate monomer unit of ethylene-vinyl acetate is 15%-28%;
in step (3), both the organic modified montmorillonite and attapulgite are modified by a y-methacryloxypropyl trimethoxy silane.
The invention has the following advantages:
The invention uses the dual compounding system of SBR and EVA
blended with inorganic nanoparticles to prepare SBR/EVA/OMMT/OATP
nanocomposites foam sole material. It showed a better mechanical property Date Recue/Date Received 2022-05-30 compared with traditional foam sole material. SBR/EVA/OMMT/OATP
nanocomposites foams showed low shrinkage, low post shrinkage, low density, moderate hardness, low compression, high stability and low cost.
Shrinkage can be reduced to 0.5-1.5%, density is 0.21-0.35 g/cm3, compression is 10-20%, hardness (Shore C) is 40-60 and post shrinkage is 5-10%.
Specific implementation mode The invention is described in detail combined with the specific implementation mode as follows:
A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams comprises following steps:
(1) mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate with 20-30 parts of white carbon black, 5.0-10.0 parts of zinc oxide and 1.0-5.0 parts of stearic acid by weight in a mixer;
(2) adding 0.5-5.0 parts of a foaming agent (azodicarbonamide), 0.1-2.0 parts of a crosslinking agent (diisopropyl peroxide), 0.5-5.0 parts of sulfur and promoter and 0.5-5.5 parts of paraffin by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with ratio of 1:10-10:1 into an internal mixer together with the mixture obtained in step (2);
(4) pressing the mixture obtained in step (3) into a sheet with a Date Recue/Date Received 2022-05-30 thickness of 1-5 mm by using an open two-roll mixer, and obtaining a sheet material;
(5) heating a mold embedded in a vulcanizing machine to 190-200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6) putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
in step (1), the molar ratio of styrene butadiene rubber and ethylene-vinyl acetate is 10:1-5:5.
the styrene butadiene rubber contains 22%-25% of styrene monomers, and the ethylene-vinyl acetate contains 15%-28% of vinyl acetate monomers.
in the step (2), the promoter is a mixture of tetramethylthiuram disulfide, N-cycloethy1-2-benzothiazole sulfenamide and benzothiazole disulfide; each of reagents is 0.2 parts by weight.
in the step (3), both the organic modified montmorillonite (OMMT) and the organic modified attapulgite (OATP) are modified by the silane coupling agent y-methacryloxypropyl trimethoxy silane.
Example 1:
(1)mixing 100 parts of styrene butadiene rubber/ethylene-vinyl Date Recue/Date Received 2022-05-30 acetate (10:3) with 20 parts of white carbon black and 6.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 45 rpm/min;
(2) adding 4.0 parts of a foaming agent (azodicarbonamide), 0.6 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 2.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3)adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 1:4 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material (5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene Date Recue/Date Received 2022-05-30 butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 1 are showed as follows: shrinkage is 1.0%, density is 0.22 g/cm3, compression is 18.5%, hardness (Shore C) is 42.8, rebound resilience is 50.6%, post shrinkage is 9.32%.
Example 2:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (10:3) with 25 parts of white carbon black and 9.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 45 rpm/min;
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.2 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenarnide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 3.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 5:3 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining
a styrene monomer unit in the styrene-butadiene rubber is 22%-25%, and a vinyl acetate monomer unit of ethylene-vinyl acetate is 15%-28%;
in step (3), both the organic modified montmorillonite and attapulgite are modified by a y-methacryloxypropyl trimethoxy silane.
The invention has the following advantages:
The invention uses the dual compounding system of SBR and EVA
blended with inorganic nanoparticles to prepare SBR/EVA/OMMT/OATP
nanocomposites foam sole material. It showed a better mechanical property Date Recue/Date Received 2022-05-30 compared with traditional foam sole material. SBR/EVA/OMMT/OATP
nanocomposites foams showed low shrinkage, low post shrinkage, low density, moderate hardness, low compression, high stability and low cost.
Shrinkage can be reduced to 0.5-1.5%, density is 0.21-0.35 g/cm3, compression is 10-20%, hardness (Shore C) is 40-60 and post shrinkage is 5-10%.
Specific implementation mode The invention is described in detail combined with the specific implementation mode as follows:
A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams comprises following steps:
(1) mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate with 20-30 parts of white carbon black, 5.0-10.0 parts of zinc oxide and 1.0-5.0 parts of stearic acid by weight in a mixer;
(2) adding 0.5-5.0 parts of a foaming agent (azodicarbonamide), 0.1-2.0 parts of a crosslinking agent (diisopropyl peroxide), 0.5-5.0 parts of sulfur and promoter and 0.5-5.5 parts of paraffin by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with ratio of 1:10-10:1 into an internal mixer together with the mixture obtained in step (2);
(4) pressing the mixture obtained in step (3) into a sheet with a Date Recue/Date Received 2022-05-30 thickness of 1-5 mm by using an open two-roll mixer, and obtaining a sheet material;
(5) heating a mold embedded in a vulcanizing machine to 190-200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6) putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
in step (1), the molar ratio of styrene butadiene rubber and ethylene-vinyl acetate is 10:1-5:5.
the styrene butadiene rubber contains 22%-25% of styrene monomers, and the ethylene-vinyl acetate contains 15%-28% of vinyl acetate monomers.
in the step (2), the promoter is a mixture of tetramethylthiuram disulfide, N-cycloethy1-2-benzothiazole sulfenamide and benzothiazole disulfide; each of reagents is 0.2 parts by weight.
in the step (3), both the organic modified montmorillonite (OMMT) and the organic modified attapulgite (OATP) are modified by the silane coupling agent y-methacryloxypropyl trimethoxy silane.
Example 1:
(1)mixing 100 parts of styrene butadiene rubber/ethylene-vinyl Date Recue/Date Received 2022-05-30 acetate (10:3) with 20 parts of white carbon black and 6.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 45 rpm/min;
(2) adding 4.0 parts of a foaming agent (azodicarbonamide), 0.6 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 2.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3)adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 1:4 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material (5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene Date Recue/Date Received 2022-05-30 butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 1 are showed as follows: shrinkage is 1.0%, density is 0.22 g/cm3, compression is 18.5%, hardness (Shore C) is 42.8, rebound resilience is 50.6%, post shrinkage is 9.32%.
Example 2:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (10:3) with 25 parts of white carbon black and 9.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 45 rpm/min;
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.2 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenarnide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 3.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 5:3 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining
7 Date Recue/Date Received 2022-05-30 a sheet material;
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 2 are showed as follows: shrinkage is 1.43%, density is 0.245 g/cm3, compression is 17.4%, hardness (Shore C) is 46.4, rebound resilience is 51%, post shrinkage is 7.82%.
Example 3:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (5:2) with 25 parts of white carbon black and 6.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 40 rpm/min;
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.4 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2`-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight),
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 2 are showed as follows: shrinkage is 1.43%, density is 0.245 g/cm3, compression is 17.4%, hardness (Shore C) is 46.4, rebound resilience is 51%, post shrinkage is 7.82%.
Example 3:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (5:2) with 25 parts of white carbon black and 6.0 parts of zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 40 rpm/min;
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.4 parts of a crosslinking agent (diisopropyl peroxide), 0.5 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2`-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight),
8 Date Recue/Date Received 2022-05-30 5.0 parts of paraffin and 1.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 7:3 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material;
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to fonn foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 3 are showed as follows: shrinkage is 1.1%, density is 0.237 g/cm3, compression is 15.5%, hardness (Shore C) is 48.2, rebound resilience is 52.2%, post shrinkage is 6.3%.
Example 4:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (5:5) with 20 parts of white carbon black and 6.0 parts of
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 7:3 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material;
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to fonn foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 3 are showed as follows: shrinkage is 1.1%, density is 0.237 g/cm3, compression is 15.5%, hardness (Shore C) is 48.2, rebound resilience is 52.2%, post shrinkage is 6.3%.
Example 4:
(1)mixing 100 parts of styrene butadiene rubber and ethylene-vinyl acetate (5:5) with 20 parts of white carbon black and 6.0 parts of
9 Date Recue/Date Received 2022-05-30 zinc oxide by weight in a mixer, mixer parameters: 100 C, 10 min and 30 rpm/min;
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.1 parts of a crosslinking agent (diisopropyl peroxide), 1.0 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 2.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 3:7 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material;
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
Date Recue/Date Received 2022-05-30 The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 4 are as follows: shrinkage is 1.5%, density is 0.226 g/cm3, compression is 18.6%, hardness (Shore C) is 52.2 rebound resilience is 54.6%, post shrinkage is 8.43%.
The contents of the invention are not limited to those listed in the embodiment. Any equivalent transformation of the technical scheme of the invention by ordinary technicians in the field through reading the specification of the invention shall be covered by the claims of the invention.
Date Recue/Date Received 2022-05-30
(2) adding 3.0 parts of a foaming agent (azodicarbonamide), 0.1 parts of a crosslinking agent (diisopropyl peroxide), 1.0 parts of sulfur, promoter (containing tetramethylthiuram disulfde, N-cyclohexylbenzothiazole-2-sulphenamide and 2,2'-dibenzothiazole disulfide, each of reagents is 0.2 parts by weight), 5.0 parts of paraffin and 2.0 parts of stearic acid by weight into the mixer to prepare a mixture;
(3) adding 1.0 parts of an organic modified montmorillonite and attapulgite by weight with the ratio of 3:7 into an internal mixer together with the mixture obtained in step (2);
(4)pressing the mixture obtained in step (3) into a sheet with a thickness of 3 mm by using an open two-roll mixer, and obtaining a sheet material;
(5)heating a mold embedded in a vulcanizing machine to 200 C, then evenly sprayed by polysiloxane emulsion release agent, evaporating water;
(6)putting the sheet material obtained in step (4) into the vulcanizing machine, and molding and crosslinking the sheet to form foams;
cooling to 25 C, obtaining the high shrinkage stability styrene butadiene rubber-based nanocomposite foams.
Date Recue/Date Received 2022-05-30 The properties of SBR/EVA/OMMT/OATP nanocomposite foams prepared by Example 4 are as follows: shrinkage is 1.5%, density is 0.226 g/cm3, compression is 18.6%, hardness (Shore C) is 52.2 rebound resilience is 54.6%, post shrinkage is 8.43%.
The contents of the invention are not limited to those listed in the embodiment. Any equivalent transformation of the technical scheme of the invention by ordinary technicians in the field through reading the specification of the invention shall be covered by the claims of the invention.
Date Recue/Date Received 2022-05-30
Claims
1. A method for the preparation of high shrinkage stability styrene butadiene rubber-based nanocomposite foams comprising the following steps:
(1) mixing 100 parts of styrene-butadiene rubber and ethylene-vinyl acetate, 20-30 parts of white carbon black, 5.0-10.0 parts of zinc oxide and 1.0-5.0 parts of stearic acid by weight in a mixer;
(2) adding 0.5-5.0 parts of azodicarbonamide, 0.1-2.0 parts of dicumyl peroxide, 0.5-5.0 parts of sulfur and an accelerator, and 0.5-5.5 parts paraffin wax by weight into the mixer to obtain a mixture;
(3) adding 1.0 parts by weight of organic modified montmorillonite and organic modified attapulgite with ratio of 1:10 ¨ 10:1 into the mixture in the mixer, mixing;
(4) pressing the mixture into a sheet with a thickness of 1-5 mm on an open two-roll mixer;
(5) preheating an embedded mold in a vulcanizer to 190-200 C, evenly spraying a polysiloxane water-based emulsion release agent, and drying by evaporation;
(6) putting the sheet into the vulcanizer, cross-linking and foam molding the sheet, and cooling to 25 C to obtain the high shrinkage stability styrene-butadiene rubber-based nanocomposite foams; wherein Date Recue/Date Received 2022-05-30 in step (1), a molar ratio of the styrene-butadiene rubber to the ethylene-vinyl acetate is 1:10 ¨ 5:5;
a styrene monomer unit in the styrene-butadiene rubber is 22%-25%, and a vinyl acetate monomer unit of ethylene-vinyl acetate is 15%-28%;
in step (3), both the organic modified montmorillonite and attapulgite are modified by a y-methacryloxypropyl trimethoxy silane.
2. The method according to claim 1, wherein:
in step (2), the accelerator is a mixture of tetramethylthiuram disulfide, N-cycloethy1-2-benzothiazole sulfenamide and benzothiazole disulfide, each of which is 0.2 parts by weight.
3. A foamed material prepared by the method for preparing the high shrinkage stability styrene-butadiene rubber-based nanocomposite foams according to
claim 1.
Date Recue/Date Received 2022-05-30
Date Recue/Date Received 2022-05-30
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| CN201610992994.9A CN106432842B (en) | 2016-11-11 | 2016-11-11 | Nano combined expanded material of high convergency stability butadiene-styrene rubber base and preparation method thereof |
| CN2016109929949 | 2016-11-11 | ||
| PCT/CN2017/071046 WO2018086249A1 (en) | 2016-11-11 | 2017-01-13 | Styrene-butadiene rubber based nano composite foaming material with high shrinkage stability and preparation method therefor |
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| CN109370231A (en) * | 2018-10-04 | 2019-02-22 | 南京万和新材料有限公司 | A kind of rubber-plastic foamed thermal insulation material of antibacterial hydrophobic |
| CN110128711B (en) * | 2019-05-20 | 2021-09-03 | 陕西科技大学 | Wear-resistant natural rubber-based nano composite foam material and preparation method thereof |
| CN111004432A (en) * | 2019-10-28 | 2020-04-14 | 茂泰(福建)鞋材有限公司 | Preparation method of high-performance composite sole with hollow design |
| CN111087662B (en) * | 2019-12-07 | 2022-04-01 | 福建元吉体育用品有限公司 | Ball-in-ball surface skin material and preparation method of ball-in-ball surface skin |
| CN111704755A (en) * | 2020-06-28 | 2020-09-25 | 陕西科技大学 | Preparation method of rubber foam material with bubble inner wall shell |
| CN113024960B (en) * | 2021-03-31 | 2024-02-13 | 蔡杰 | Heat-resistant, wear-resistant and high-strength modified EVA rubber-plastic foam material and preparation method thereof |
| CN113603948B (en) * | 2021-08-27 | 2023-03-31 | 温州市巨创鞋材有限公司 | Wear-resistant elastic sole and preparation process thereof |
| CN116102814A (en) * | 2021-11-11 | 2023-05-12 | 茂泰(福建)鞋材有限公司 | Ultra-light shock absorption EVA sole and preparation process thereof |
| CN114085438B (en) * | 2021-11-19 | 2022-07-19 | 温州市耀阳鞋业有限公司 | Anti-slip men's shoes and preparation method thereof |
| CN114316339A (en) * | 2021-12-07 | 2022-04-12 | 茂泰(福建)鞋材有限公司 | Antibacterial EVA (ethylene-vinyl acetate copolymer) foamed sole and preparation method thereof |
| CN115746538A (en) * | 2022-10-10 | 2023-03-07 | 福建美明达鞋业发展有限公司 | Shock-absorbing sneaker sole and preparation process thereof |
| CN116285360B (en) * | 2023-03-15 | 2023-09-19 | 东莞市富颖电子材料有限公司 | Silica gel for intelligent wearing product and preparation method thereof |
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| CN101555332B (en) * | 2009-05-05 | 2011-08-17 | 陕西科技大学 | Modified EVA microporous elastomer composite material and preparation method thereof |
| CN102993545B (en) * | 2012-08-13 | 2016-05-11 | 茂泰(福建)鞋材有限公司 | Be used for anti-skidding high wear-resistant rubber material of light weight of sole and preparation method thereof |
| CN102863644B (en) * | 2012-10-23 | 2013-12-11 | 南通市黄海电机有限公司 | Process for preparing polymer rubber |
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