CN102504362B - Sizing material for rubber shoe sole and preparation method thereof - Google Patents
Sizing material for rubber shoe sole and preparation method thereof Download PDFInfo
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- CN102504362B CN102504362B CN201110390109.7A CN201110390109A CN102504362B CN 102504362 B CN102504362 B CN 102504362B CN 201110390109 A CN201110390109 A CN 201110390109A CN 102504362 B CN102504362 B CN 102504362B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 92
- 239000005060 rubber Substances 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000004513 sizing Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003801 milling Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 13
- 238000002203 pretreatment Methods 0.000 claims description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims description 11
- 229920003052 natural elastomer Polymers 0.000 claims description 11
- 229920001194 natural rubber Polymers 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 10
- 235000019241 carbon black Nutrition 0.000 claims description 7
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- -1 2-5 parts Chemical compound 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 claims description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002357 guanidines Chemical class 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 claims description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 235000020610 powder formula Nutrition 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000013536 elastomeric material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a sizing material for a rubber shoe sole and a preparation method thereof. The sizing material comprises the following raw materials for preparing active ingredients in parts by weight: 100 parts of rubber, 1.2-2.5 parts of sulfur, 2-5 parts of zinc oxide, 1-2.5 parts of stearic acid, 1-3 parts of a medium-speed accelerant, 0.3 part of a high-speed accelerant, 1.5-3 parts of an anti-ageing agent, 35-55 parts of carbon black, 5-10 parts of softening oil, 25-35 parts of rubber powder and 1-1.5 parts of coupling agent. The preparation method comprises the following steps of: pretreating the rubber powder; plastifying rubber; compounding; milling, and the like. The rubber shoe sole produced by using a rubber powder formula and the preparation method thereof has the advantages of reduction in the tensile strength change rate by 3-5 percent, reduction in the tensile yield change rate by 5-8 percent, the same wear resistance and bending resistance as those of a rubber shoe sole produced without using rubber powder in the same type of products, smooth appearance handfeel, soft brightness and increase in grade. The sizing material is suitable for preparing rubber shoe soles of dress shoes and outdoor shoes.
Description
Technical field
The invention belongs to rubber item field, relate to the recycling of waste old, specifically a kind of sizing material for rubber shoe sole.
Technical background
Along with China's elastomeric material usage quantity increases day by day, the processing problem of waste rubber goods is also more and more outstanding, if can not properly utilize, not only can cause very big burden to environment, causes the waste of resource simultaneously.
At present, the regeneration approach of waste old material, mainly contains two aspects: the one, make rubber powder for aspects such as building asphalt modifications; The 2nd, make reclaimed rubber, add material as low grade and produce for rubber item.Rubber powder is the Powdered elastomeric material that rubber item obtains through grinding and processing processing, general rubber powder is mainly applied in low-grade goods, is widely used in the fields such as physical culture plastic sports ground, recreation ground, rubber floor tile, waterproof roll, waterproof paint, highway modifying asphalt, rubber item.
There is following problem in above-mentioned two approach:
1, produce in reclaimed rubber process at waste old, can produce the environmental pollution such as waste water, waste gas;
2, reclaimed rubber is mainly used in low-grade rubber item production, and rubber powder is mainly used in construction field, has limited to a certain extent rubber regeneration and has utilized scale and utilize benefit, thereby affected the enthusiasm of waste old process for producing.
Summary of the invention
The technical problem to be solved in the present invention, be to provide a kind of sizing material for rubber shoe sole and preparation method thereof, realize the relatively large use of rubber powder in medium-to-high grade rubber soles is produced, guaranteed that on the basis of sole quality, performance ageing-resistant to rubber soles, outward appearance sense of touch improves to some extent.Make the tensile strength velocity of variation of sole reduce by 3% ~ 5%, tensile yield velocity of variation reduces by 5% ~ 8%; With in like product, do not use the wear resisting property of the prepared rubber soles of rubber powder, resistance to bending performance identical, and outward appearance feel is smooth, brightness is soft, class improves.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of sizing material for rubber shoe sole, the raw material of making effective constituent comprises in parts by weight:
100 parts of rubber, 1.2-2.5 parts, sulphur,
2-5 parts, zinc oxide, 1-2.5 parts of stearic acid,
1-3 parts of moderate accelerators, 0.3 part of quick acting accelerator,
1.5-3 parts, anti-aging agent, 35-55 parts of carbon blacks,
5-10 parts of softening oils, 25-35 parts of rubber powders,
1-1.5 parts of coupling agents.
As a kind of restriction of the present invention, described rubber is the combination of any one or at least two kinds in natural rubber, styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber;
Described moderate accelerator is a kind of in sulfenamide moderate accelerator, thiazoles moderate accelerator or guanidine class moderate accelerator or the mixture at least two kinds;
Described quick acting accelerator is thiurams quick acting accelerator;
Described anti-aging agent is at least one in p phenylenediamine type antioxidant or phenol anti-aging agent;
Described coupling agent is silane coupling agent;
Described softening oil is petroleum softening oil.
As further restriction, described moderate accelerator is N-cyclohexyl-2-[4-morpholinodithio base sulphenamide, dibenzothiazyl disulfide or vulkacit D;
Described thiurams quick acting accelerator is tetramethyl-thiuram disulfide;
Described anti-aging agent is N-sec.-propyl-N ＇-diphenyl-para-phenylene diamine or 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol);
Described silane coupling agent is γ mercaptopropyitrimethoxy silane;
Described softening oil is high aromatic oil or paraffin oil.
The present invention also provides the preparation method of above-mentioned sizing material for rubber shoe sole, carries out according to following steps order:
1, rubber powder pre-treatment: rubber powder, coupling agent are dropped into milling machine, at 50-60 ℃, stir 5min with the rotating speed of 20-35rpm/min, discharging is dried in the air to room temperature, obtains pre-treatment rubber powder, for subsequent use;
2, rubber plastic steelmaking: rubber is plasticated, controls William's plasticity 0.40 ± 0.05, obtains softened rubber;
3, mixing: to use mixer mixing, will in above-mentioned softened rubber, add zinc oxide and stearic acid, moderate accelerator, mixing 1.5 minutes; Then add step 1 gained pre-treatment rubber powder, after mixing 1-1.5min, then add anti-aging agent, carbon black, softening oil, mixing to evenly rear Banbury mixer discharge, obtain mixing of rubber;
4, the glue stuff compounding that step 3 obtains, uses mill, adds vulcanizing agent and quick acting accelerator, mixes, and obtains product.
Owing to having adopted above-mentioned technical scheme, the invention technological progress is:
To after rubber powder pre-treatment, carry out again the preparation of sizing material, realized the relatively large use of rubber powder in medium-to-high grade rubber soles is produced, guaranteeing, on the basis of sole quality, to have realized improvement in performance ageing-resistant to rubber soles, outward appearance sense of touch.Thermal ageing 12 hours in 100 ℃ of situations after testing, its tensile strength velocity of variation reduces by 3%-5%, and tensile yield velocity of variation reduces by 5%-8%; With in like product, do not use the wear resisting property of the prepared rubber soles of rubber powder, resistance to bending performance identical, and outward appearance feel is smooth, brightness is soft, class improves.
The present invention is applicable to the preparation of dress shoes and outdoor shoe rubber soles.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
Embodiment
The raw material of making its effective constituent, comprises in parts by weight:
Embodiment 1-3 uses modifying rubber powder rubber mass at the bottom of being respectively a kind of dress shoes glue, and shown in formula sees the above table, their preparation methods separately carry out according to following steps order respectively:
(1) rubber powder pre-treatment: rubber powder, coupling agent are dropped into milling machine, at 50 ℃, stir 5min with the rotating speed of 20rpm/min, discharging is dried in the air to room temperature, for subsequent use.
(2) natural rubber is plasticated, and controls William's plasticity 0.40 ± 0.05; After plasticating, natural rubber, according to formula, mixes with cis-1,4-polybutadiene rubber.
(3) mixing process: use mixer mixing; The blend glue stuff of the above-mentioned natural rubber mixing and cis-1,4-polybutadiene rubber adds zinc oxide and stearic acid, moderate accelerator, mixing 1.5 minutes; Then add the pre-treatment rubber powder in step (1), after mixing 1min, then add anti-aging agent, carbon black, softening oil, mixing to evenly rear Banbury mixer discharge.
(4) glue stuff compounding that step (3) obtains, uses mill, adds sulphur and quick acting accelerator, mixes, and has both obtained product.
Embodiment 4-5 is respectively a kind of outdoor shoe rubber soles modifying rubber powder rubber mass, and as shown in Table, its preparation method carries out according to following steps order respectively for their formula separately:
(1) rubber powder pre-treatment: rubber powder, coupling agent are dropped into milling machine, at 60 ℃, stir 5min with the rotating speed of 35rpm/min, discharging is dried in the air to room temperature, for subsequent use.
(2) natural rubber is plasticated, and controls William's plasticity 0.40 ± 0.05; After plasticating, natural rubber, according to formula, mixes with styrene-butadiene rubber(SBR).
(3) mixing process: use mixer mixing; The blend glue stuff of the above-mentioned natural rubber mixing and styrene-butadiene rubber(SBR) adds zinc oxide and stearic acid, moderate accelerator, mixing 1.5 minutes; Then add the pre-treatment rubber powder in step (1), after mixing 1.5min, then add anti-aging agent, high wear-resistant carbon black, softening oil, mixing to evenly rear Banbury mixer discharge.
(4) glue stuff compounding that step (3) obtains, uses mill, adds sulphur and quick acting accelerator, mixes, and has both obtained product.
Embodiment 6 is a kind of outdoor shoe rubber soles modifying rubber powder rubber mass, and as shown in Table, its preparation method carries out according to following steps order formula:
(1) rubber powder pre-treatment: rubber powder, coupling agent are dropped into milling machine, at 60 ℃, stir 5min with the rotating speed of 35rpm/min, discharging is dried in the air to room temperature, for subsequent use.
(2) natural rubber is plasticated, and controls William's plasticity 0.40 ± 0.05; After plasticating, natural rubber, according to formula, mixes with styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber.
(3) mixing process: use mixer mixing; The blend glue stuff of the above-mentioned natural rubber mixing, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber adds zinc oxide and stearic acid, moderate accelerator, mixing 1.5 minutes; Then add the pre-treatment rubber powder in step (1), after mixing 1.5min, then add anti-aging agent, high wear-resistant carbon black, softening oil, mixing to evenly rear Banbury mixer discharge.
(4) glue stuff compounding that step (3) obtains, uses mill, adds sulphur and quick acting accelerator, mixes, and obtains product.
Claims (3)
1. a sizing material for rubber shoe sole,
it is characterized in thatthe raw material of making effective constituent comprises in parts by weight:
100 parts of rubber, 1.2-2.5 parts, sulphur,
2-5 parts, zinc oxide, 1-2.5 parts of stearic acid,
1-3 parts of moderate accelerators, 0.3 part of quick acting accelerator,
1.5-3 parts, anti-aging agent, 35-55 parts of carbon blacks,
5-10 parts of softening oils, 25-35 parts of rubber powders,
1-1.5 parts of coupling agents;
It carries out according to following steps order:
(1) rubber powder pre-treatment: rubber powder, coupling agent are dropped into milling machine, at 50-60 ℃, stir 5min with the rotating speed of 20-35rpm/min, discharging is dried in the air to room temperature, obtains pre-treatment rubber powder, for subsequent use;
(2) rubber plastic steelmaking: rubber is plasticated, controls William's plasticity 0.40 ± 0.05, obtains softened rubber;
(3) mixing: to use mixer mixing, will in above-mentioned softened rubber, add zinc oxide and stearic acid, moderate accelerator, mixing 1.5 minutes; Then add step 1 gained pre-treatment rubber powder, after mixing 1-1.5min, then add anti-aging agent, carbon black, softening oil, mixing to evenly rear Banbury mixer discharge, obtain glue stuff compounding;
(4) open refining: the glue stuff compounding that step 3 obtains, use mill, add vulcanizing agent and quick acting accelerator, mix, obtain product.
2. sizing material for rubber shoe sole according to claim 1,
it is characterized in thatdescribed rubber is: at least one in natural rubber, styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber;
Described moderate accelerator is at least one in sulfenamide moderate accelerator, thiazoles moderate accelerator or guanidine class moderate accelerator;
Described quick acting accelerator is thiurams quick acting accelerator;
Described anti-aging agent is at least one in p phenylenediamine type antioxidant or phenol anti-aging agent;
Described coupling agent is silane coupling agent;
Described softening oil is petroleum softening oil.
3. sizing material for rubber shoe sole according to claim 2,
it is characterized in that:
Described moderate accelerator is N-cyclohexyl-2-[4-morpholinodithio base sulphenamide, dibenzothiazyl disulfide or vulkacit D;
Described quick acting accelerator is tetramethyl-thiuram disulfide;
Described anti-aging agent is N-sec.-propyl-N ＇-diphenyl-para-phenylene diamine or 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol);
Described silane coupling agent is γ mercaptopropyitrimethoxy silane;
Described softening oil is high aromatic oil or paraffin oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110390109.7A CN102504362B (en) | 2011-11-30 | 2011-11-30 | Sizing material for rubber shoe sole and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110390109.7A CN102504362B (en) | 2011-11-30 | 2011-11-30 | Sizing material for rubber shoe sole and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102504362A CN102504362A (en) | 2012-06-20 |
| CN102504362B true CN102504362B (en) | 2014-05-21 |
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| TWI593554B (en) * | 2016-08-26 | 2017-08-01 | Application of single-sided plastic powder glue on the shoe method | |
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| CN109456515A (en) * | 2018-11-19 | 2019-03-12 | 陶伟珍 | A kind of wearability sole rubber material and preparation method thereof |
| CN111040262A (en) * | 2019-12-26 | 2020-04-21 | 瑞安市大虎鞋业有限公司 | Formula of foamed rubber for manufacturing light soles |
| CN111423631A (en) * | 2020-04-26 | 2020-07-17 | 芜湖风雪橡胶有限公司 | Antistatic rubber product and preparation method thereof |
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| CN114181441A (en) * | 2021-12-25 | 2022-03-15 | 浙江恒诚鞋业有限公司 | Ice surface anti-slip sole and preparation method thereof |
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| CN102504362A (en) | 2012-06-20 |
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