CN111533967B - Rubber sole and preparation method thereof - Google Patents
Rubber sole and preparation method thereof Download PDFInfo
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- CN111533967B CN111533967B CN202010546502.XA CN202010546502A CN111533967B CN 111533967 B CN111533967 B CN 111533967B CN 202010546502 A CN202010546502 A CN 202010546502A CN 111533967 B CN111533967 B CN 111533967B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 34
- 239000005060 rubber Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 19
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 17
- 229920001194 natural rubber Polymers 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 6
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 6
- 235000019808 microcrystalline wax Nutrition 0.000 claims abstract description 6
- 239000004200 microcrystalline wax Substances 0.000 claims abstract description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 6
- 239000008117 stearic acid Substances 0.000 claims abstract description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000004636 vulcanized rubber Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010734 process oil Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 8
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical group C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 4
- DFWCPLGXFMSUCW-UHFFFAOYSA-N 3-(dimethylamino)propyl carbamimidothioate;hydron;dichloride Chemical compound Cl.Cl.CN(C)CCCSC(N)=N DFWCPLGXFMSUCW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 230000000386 athletic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber sole and a preparation method thereof, wherein the rubber sole is prepared from the following raw materials in parts by weight: 50 parts of butadiene rubber; 30 parts of styrene butadiene rubber; 10 parts of natural rubber; 5-10 parts of epoxidized trans-natural rubber; 5 parts of zinc oxide; stearic acid, 2 parts; 0.5 part of anti-aging agent RD; 0.5 part of anti-aging agent 4010 NA; 45-55 parts of white carbon black; 7-10 parts of operating oil; 1 part of microcrystalline wax; 4-5 parts of a silane coupling agent Si 69; 1.5 parts of accelerator DM; 0.5 part of promoter TMTD; insoluble sulfur, 2 parts. The material is prepared by mixing, cooling, standing and vulcanizing. The sole material prepared by the method has the advantages of good wet skid resistance, excellent wear resistance, good flex performance and the like, and improves the safety and the service life of shoe products.
Description
Technical Field
The invention relates to a rubber sole and a preparation method thereof, belonging to the technical field of rubber shoe material production.
Background
Shoes are necessities of life. People have both aesthetic property and practicability for the quality requirements of shoes. For athletic shoes such as running shoes and basketball shoes, the wear resistance and slip resistance of the sole are two of the main performance criteria of concern. For casual shoes, children's shoes, etc., sole flexibility is one of the main performance indicators of concern. Different shoes have different performance requirements, and the same sole material is difficult to meet the performance requirements. Professor Gem, in patent CN 103059353A, teaches that the use of epoxidized trans-natural rubber in tires provides a balance of wet skid resistance, abrasion resistance and rolling resistance. In the fatigue and dynamic performance of epoxidized trans-isoprene rubber/natural rubber blend (polymer material science and engineering, 29 vol.29, 9 th page 44-47) professor of yaosmunda and the like, the epoxidized trans-isoprene rubber with the epoxy degree of less than 20% is used in combination with the natural rubber, so that the flexibility of the material can be obviously improved. However, there are few documents such as articles and patents relating to the application of trans-epoxidized natural rubber to shoe sole materials.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a rubber sole with wet skid resistance, wear resistance and flexibility.
The invention provides a rubber sole which is prepared from the following raw materials in parts by weight:
50 parts of butadiene rubber, 30 parts of styrene-butadiene rubber, 10 parts of natural rubber, 5-10 parts of epoxidized trans-natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of antioxidant RD, 0.5 part of antioxidant 4010NA, 45-55 parts of white carbon black, 7-10 parts of process oil, 1 part of microcrystalline wax, 5-5 parts of silane coupling agent Si 694, 1.5 parts of accelerator DM, 0.5 part of accelerator TMTD and 2 parts of insoluble sulfur.
The epoxy degree of the epoxidized trans-natural rubber is 13-20%.
The anti-aging agent RD is a 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
The anti-aging agent 4010NA is N-isopropyl-N' -phenyl-p-phenylenediamine.
The white carbon black is precipitated white carbon black.
The process oil is a naphthenic oil.
The silane coupling agent Si69 is bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.
The accelerator DM is 2,2' -dithiodibenzothiazole.
The promoter TMTD is tetramethyl thiuram disulfide.
In addition, the invention also provides a preparation method of the rubber sole, which comprises the following steps:
(1) preparing a rubber compound: the mixing adopts a two-stage mixing process, and the temperature of an internal mixer is set to be 115 ℃ in the first stage; all raw materials except the accelerator DM, the accelerator TMTD and insoluble sulfur in the formula are added, and are subjected to banburying for 9 minutes and then discharged; adding the rubber compound obtained in the first mixing stage into an internal mixer with circulating water cooling, adding an accelerator DM, an accelerator TMTD and insoluble sulfur, continuously mixing for 15 minutes, and discharging;
(2) cooling the rubber compound: tabletting the mixed material by a tablet machine, cutting the mixed material into required sizes by a cutting machine, and standing for 24 hours;
(3) preparing vulcanized rubber: the vulcanization temperature is 150 ℃, the vulcanization pressure is 16 MPa, and the vulcanization time is 3-8 minutes.
Has the advantages that: the invention develops a sole material with wet skid resistance, wear resistance and flexibility. The abrasion of the Akron reaches 0.20 cm3The/1.61 km, the 6-level flexion lifting rate reaches more than 40%, and the safety and the service life of the shoe product are improved.
Detailed Description
The present invention will be further described in detail with reference to the following examples for better understanding of the present invention, but the scope of the present invention as claimed is not limited to the scope shown in the examples.
Example 1
A rubber sole is prepared from the following raw materials in parts by weight: 50 parts of butadiene rubber; 30 parts of styrene butadiene rubber; 10 parts of natural rubber; 5 parts of epoxidized trans-natural rubber (the epoxy degree is 17.5 percent); 5 parts of zinc oxide; stearic acid, 2 parts; 0.5 part of anti-aging agent RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer); 0.5 part of anti-aging agent 4010NA (N-isopropyl-N' -phenyl-p-phenylenediamine); 45 parts of white carbon black; 7 parts of operating oil; 1 part of microcrystalline wax; 4 parts of silane coupling agent Si69 (bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide); accelerator DM (2,2' -dithiodibenzothiazole), 1.5 parts; 0.5 part of accelerator TMTD (tetramethylthiuram disulfide); insoluble sulfur, 2 parts.
The preparation process of the rubber sole comprises the following steps: (1) preparing a rubber compound: the mixing adopts a two-stage mixing process. In the first stage, the temperature of an internal mixer is set to be 115 ℃; all the raw materials except the accelerator DM, the accelerator TMTD and the insoluble sulfur in the formula are added, and are internally mixed for 9 minutes and then discharged; adding the rubber compound obtained in the first mixing stage into an internal mixer with circulating water cooling, adding an accelerator DM, an accelerator TMTD and insoluble sulfur, continuously mixing for 15 minutes, and discharging; (2) cooling the rubber compound: tabletting the mixed material by a tablet machine, cutting the mixed material into required size by a cutting machine, and standing for 24 hours; (3) preparing vulcanized rubber: the vulcanization temperature is 150 ℃, the vulcanization pressure is 16 MPa, and the vulcanization time is 8 minutes.
Example 2
A rubber sole is prepared from the following raw materials in parts by weight: 50 parts of butadiene rubber; 30 parts of styrene butadiene rubber; 10 parts of natural rubber; 10 parts of epoxidized trans-natural rubber (the epoxy degree is 17.5 percent); 5 parts of zinc oxide; stearic acid, 2 parts; 0.5 part of anti-aging agent RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer); 0.5 part of anti-aging agent 4010NA (N-isopropyl-N' -phenyl-p-phenylenediamine); 45 parts of white carbon black; 10 parts of operating oil; 1 part of microcrystalline wax; 5 parts of silane coupling agent Si69 (bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide); accelerator DM (2,2' -dithiodibenzothiazole), 1.5 parts; 0.5 part of accelerator TMTD (tetramethylthiuram disulfide); insoluble sulfur, 2 parts.
The preparation process of the rubber sole comprises the following steps: (1) preparing a rubber compound: the mixing adopts a two-stage mixing process. In the first stage, the temperature of an internal mixer is set to be 115 ℃; all the raw materials except the accelerator DM, the accelerator TMTD and the insoluble sulfur in the formula are added, and are internally mixed for 9 minutes and then discharged; adding the rubber compound obtained in the first-stage mixing into an internal mixer with circulating water cooling, adding the accelerator DM, the accelerator TMTD and insoluble sulfur, continuously mixing for 15 minutes, and discharging; (2) cooling the rubber compound: tabletting the mixed material by a tablet machine, cutting the mixed material into required size by a cutting machine, and standing for 24 hours; (3) preparing vulcanized rubber: the vulcanization temperature is 150 ℃, the vulcanization pressure is 16 MPa, and the vulcanization time is 3 minutes.
Comparative example 1
A rubber sole is prepared from the following raw materials in parts by weight: 50 parts of butadiene rubber; 30 parts of styrene butadiene rubber; 10 parts of natural rubber; 5 parts of zinc oxide; stearic acid, 2 parts; 0.5 part of anti-aging agent RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer); 0.5 part of anti-aging agent 4010NA (N-isopropyl-N' -phenyl-p-phenylenediamine); 45 parts of white carbon black; 7 parts of operating oil; 1 part of microcrystalline wax; 4 parts of silane coupling agent Si69 (bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide); accelerator DM (2,2' -dithiodibenzothiazole), 1.5 parts; 0.5 part of accelerator TMTD (tetramethylthiuram disulfide); insoluble sulfur, 2 parts.
The preparation process of the rubber sole comprises the following steps: (1) preparing a rubber compound: the mixing adopts a two-stage mixing process. In the first stage, the temperature of an internal mixer is set to be 115 ℃; all the raw materials except the accelerator DM, the accelerator TMTD and the insoluble sulfur in the formula are added, and are internally mixed for 9 minutes and then discharged; adding the rubber compound obtained in the first mixing stage into an internal mixer with circulating water cooling, adding an accelerator DM, an accelerator TMTD and insoluble sulfur, continuously mixing for 15 minutes, and discharging; (2) cooling the rubber compound: tabletting the mixed material by a tablet machine, cutting the mixed material into required size by a cutting machine, and standing for 24 hours; (3) preparing vulcanized rubber: the vulcanization temperature is 150 ℃, the vulcanization pressure is 16 MPa, and the vulcanization time is 8 minutes.
The main physical and mechanical properties of the sole materials prepared according to the examples and comparative examples are shown in Table 1.
TABLE 1 Main physical and mechanical Properties of the sole Material
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and it should be understood that modifications and equivalents may be made thereto by those skilled in the art without departing from the scope of the present invention.
Claims (4)
1. The rubber sole is characterized by being prepared from the following raw materials in parts by weight:
50 parts of butadiene rubber, 30 parts of styrene-butadiene rubber, 10 parts of natural rubber, 5-10 parts of epoxidized trans-natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of antioxidant RD, 0.5 part of antioxidant 4010NA, 45-55 parts of white carbon black, 7-10 parts of process oil, 1 part of microcrystalline wax, 5-5 parts of silane coupling agent Si 694, 1.5 parts of accelerator DM, 0.5 part of accelerator TMTD and 2 parts of insoluble sulfur; the epoxy degree of the epoxidized trans-natural rubber is 13-20%.
2. The rubber sole according to claim 1, wherein the white carbon black is precipitated white carbon black.
3. A rubber shoe sole according to claim 1, wherein said process oil is a naphthenic oil.
4. A method for preparing a rubber sole as claimed in any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) preparing a rubber compound: the mixing adopts a two-stage mixing process, and the temperature of an internal mixer is set to be 115 ℃ in the first stage; all the raw materials except the accelerator DM, the accelerator TMTD and the insoluble sulfur in the formula are added, and are internally mixed for 9 minutes and then discharged; adding the rubber compound obtained in the first mixing stage into an internal mixer with circulating water cooling, adding an accelerator DM, an accelerator TMTD and insoluble sulfur, continuously mixing for 15 minutes, and discharging;
(2) cooling the rubber compound: tabletting the mixed material by a tablet machine, cutting the mixed material into required size by a cutting machine, and standing for 24 hours;
(3) preparing vulcanized rubber: the vulcanization temperature is 150 ℃, the vulcanization pressure is 16 MPa, and the vulcanization time is 3-8 minutes.
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CN202010546502.XA CN111533967B (en) | 2020-06-16 | 2020-06-16 | Rubber sole and preparation method thereof |
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CN202010546502.XA CN111533967B (en) | 2020-06-16 | 2020-06-16 | Rubber sole and preparation method thereof |
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CN111533967A CN111533967A (en) | 2020-08-14 |
CN111533967B true CN111533967B (en) | 2022-05-17 |
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Families Citing this family (3)
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CN112679871B (en) * | 2020-12-25 | 2023-06-06 | 安踏(中国)有限公司 | Composite rubber, preparation method thereof and sole material |
CN114524983B (en) * | 2022-01-21 | 2024-03-29 | 茂泰(福建)新材料科技有限公司 | Anti-cracking environment-friendly rubber sole and preparation method thereof |
CN114456454A (en) * | 2022-02-14 | 2022-05-10 | 上海汇平化工有限公司 | Wear-resistant shoe material and preparation method thereof |
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