CN110643084A - Enhancement mode antiskid sole and antiskid shoes - Google Patents
Enhancement mode antiskid sole and antiskid shoes Download PDFInfo
- Publication number
- CN110643084A CN110643084A CN201911006889.3A CN201911006889A CN110643084A CN 110643084 A CN110643084 A CN 110643084A CN 201911006889 A CN201911006889 A CN 201911006889A CN 110643084 A CN110643084 A CN 110643084A
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- solution
- sole
- modified zirconia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004113 Sepiolite Substances 0.000 claims abstract description 20
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 20
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 20
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 17
- 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 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 31
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- YXWFTAHVYOBABK-UHFFFAOYSA-N 3-isocyanatopropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCN=C=O YXWFTAHVYOBABK-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004073 vulcanization Methods 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
- C08L7/00—Compositions of natural rubber
-
- 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
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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 an enhanced anti-skidding sole and an anti-skidding shoe, which have the technical scheme that the enhanced anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of 80-00 parts by weight of natural rubber; 10-50 parts of styrene butadiene rubber; 1-4 parts of an accelerator; 0.1-0.5 part of antioxidant; 2.5-4.5 parts of an active agent; 2-10 parts of sulfur; 6-30 parts of a filler; the filler is composed of the following substances in parts by weight: 5-20 parts of modified zirconia; 1-10 parts of activated sepiolite, and the invention has the beneficial effects that the modified zirconia and the activated sepiolite are added in the formula, so that the dry friction coefficient and the wet friction coefficient are improved, and the integral anti-skid performance is improved.
Description
Technical Field
The invention relates to the field of shoes, in particular to an enhanced anti-skidding sole and an anti-skidding shoe.
Background
Shoes are indispensable equipment in daily life. In some wet workplaces, such as kitchens, bathrooms or roads in rainy and snowy weather, people are inconvenient to walk and easy to slip, or on dry-laid marble floors, the ground is easy to slip accidentally because the ground is too smooth.
At present, some sports shoes or slippers are provided with deeper grains on soles, but the effect is limited, the soles are mostly made of natural rubber materials as main components, and although the natural rubber has certain anti-skid performance, the anti-skid performance can not meet the requirements of the sole materials of high-grade sports shoes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an enhanced anti-skidding sole and an anti-skidding shoe.
In order to achieve the purpose, the invention provides the following technical scheme: the enhanced anti-skidding sole and the enhanced anti-skidding shoes comprise the anti-skidding sole, wherein the anti-skidding sole consists of the following substances in parts by weight:
80-00 parts of natural rubber;
10-50 parts of styrene butadiene rubber;
1-4 parts of an accelerator;
0.1-0.5 part of antioxidant;
2.5-4.5 parts of an active agent;
2-10 parts of sulfur;
6-30 parts of a filler;
the filler is composed of the following substances in parts by weight:
5-20 parts of modified zirconia;
1-10 parts of activated sepiolite.
As a further improvement of the invention, the preparation method of the modified zirconia comprises the following steps:
the method comprises the following steps: mixing 10-100 parts by weight of ethanol, 100-800 parts by weight of silane coupling agent and 10-100 parts by weight of deionized water, dropwise adding 1-10 parts by weight of acid solution to adjust the pH value of the mixed solution to 5, and stirring for 2-16 hours;
step two: under the protection of inert gas, adding 10-200 parts by weight of zirconia and 1-20 parts by weight of the mixed solution into 100-2000 parts by weight of toluene solution, stirring for 2-16 hours, obtaining modified zirconia through centrifugal separation, cleaning the modified zirconia, and drying to constant weight;
step three: emulsifying a mixed solution of 10-100 parts by weight of the modified zirconia, 2-20 parts by weight of sodium dodecyl sulfate, 1-30 parts by weight of hexadecanol and 10-1000 parts by weight of deionized water, adding 2-20 parts by weight of ammonium persulfate solution, heating to 70-80 ℃, dropwise adding 20-600 parts by weight of acrylate monomer emulsion into the mixed solution, preserving heat for 1-4 hours after dropwise adding, performing suction filtration, and performing vacuum drying at 100 ℃ to obtain the acrylic ester monomer emulsion.
As a further improvement of the invention, the preparation method of the activated sepiolite comprises the following steps:
step (1): mixing and stirring 10-100 parts by weight of ethanol, 12-120 parts by weight of polyvinyl alcohol and 200-2000 parts by weight of deionized water for 1-3 hours, dropwise adding 1-10 parts by weight of alkaline solution to adjust the pH value of the mixed solution to 8.5, heating to 30-50 ℃, and stirring for 0.5-1 hour;
step (2): and dropwise adding 2-20 parts by weight of ammonium persulfate solution into the mixed solution, stirring for 2 hours after dropwise adding, performing suction filtration, and performing vacuum drying at 100 ℃ to obtain the ammonium persulfate solution.
In a further improvement of the present invention, in the first step, the silane coupling agent is any one of vinyltriethoxysilane, isocyanatopropyltrimethylsilane, aminopropyltriethoxysilane, and vinyltrimethoxysilane.
As a further improvement of the present invention, in the first step, the acidic solution is any one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the third step, the acrylic ester monomer is any one or a mixture of more than one of methyl acrylate monomer, ethyl acrylate monomer, methyl methacrylate monomer, hydroxyethyl acrylate monomer and hydroxypropyl acrylate monomer.
In a further improvement of the present invention, in the step (1), the alkaline solution is any one of ammonia water, a sodium hydroxide solution and a potassium hydroxide solution.
As a further improvement of the present invention, in the step (1), after completion of the stirring, the mixture was allowed to stand for 15 minutes and then subjected to ultrasonic treatment at 300W for 2 minutes.
A preparation method of an enhanced anti-skid sole and an anti-skid shoe comprises the following steps:
step (a): plasticating natural rubber and styrene butadiene rubber on an open mill;
step (b): sequentially adding activated sepiolite, an antioxidant, an active agent and modified zirconia, mixing in an internal mixer, uniformly discharging, wherein the mixing temperature is 75-80 ℃, and the mixing time is 10-12 minutes;
step (c): and (c) standing the mixed material obtained in the step (b) for 15-20 hours, transferring and placing the mixed material in an open mill, adding an accelerator and sulfur, vulcanizing by using a vulcanizing machine, and discharging to obtain a vulcanized rubber sample.
The invention has the beneficial effects that:
1. the hydrophilicity of the zirconium oxide is increased through surface modification treatment of the zirconium oxide, when the sole is rubbed, the hydrophilic zirconium oxide can easily puncture a water film, and the sole can be quickly contacted with a friction surface, so that the wet friction coefficient is increased;
2. the introduction of the activated sepiolite increases the adhesive force between the film and the friction surface, so that the dry friction coefficient mainly based on the adhesive friction force is increased in a dry state;
3. the modified zirconia is dispersed in the rubber sheet, so that the polarity of the surface of the rubber sheet is increased, and a strong adhesion effect can be generated under the synergistic effect of the modified zirconia and the activated sepiolite, so that the adhesion friction of rubber in contact with a friction surface is increased, and the dry friction coefficient is greatly improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of the following substances in parts by weight:
80 parts of natural rubber;
10 parts of styrene butadiene rubber;
1 part of an accelerator;
0.1 part of antioxidant;
2.5 parts of an active agent;
2 parts of sulfur;
5 parts of modified zirconia;
1 part of activated sepiolite.
The preparation method of the modified zirconia comprises the following steps:
the method comprises the following steps: mixing 10 parts by weight of ethanol, 100 parts by weight of vinyl trimethoxy silane and 10 parts by weight of deionized water, and dropwise adding 1-10 parts by weight of hydrochloric acid solution to adjust the pH of the mixed solution to 5, wherein the rotating speed is 300 r/m, and the stirring time is 2 hours;
step two: under the protection of nitrogen, adding 10 parts by weight of zirconia and 1 part by weight of the mixed solution into 100 parts by weight of toluene solution, stirring at the rotating speed of 300 r/m for 2 hours, obtaining modified zirconia through centrifugal separation, cleaning the modified zirconia with ethanol solution, and drying at 70 ℃ to constant weight;
step three: ultrasonically emulsifying a mixed solution of 10 parts by weight of the modified zirconia, 2 parts by weight of sodium dodecyl sulfate, 1 part by weight of hexadecanol and 10 parts by weight of deionized water, carrying out ultrasonic treatment at the ultrasonic frequency of 200kHz and the output power of 300W for 30 minutes, adding 2 parts by weight of ammonium persulfate solution, heating to 70 ℃, dropwise adding 20 parts by weight of methyl acrylate monomer emulsion into the mixed solution at the speed of 0.01 part by weight/minute, carrying out heat preservation for 1 hour after dropwise adding, carrying out suction filtration, and carrying out vacuum drying at the temperature of 100 ℃ to obtain the modified zirconia.
The preparation method of the activated sepiolite comprises the following steps:
step (1): mixing 10 parts by weight of ethanol, 12 parts by weight of polyvinyl alcohol and 200 parts by weight of deionized water, stirring for 1 hour at the rotating speed of 2800r/min, standing for 18 minutes, treating for 2 minutes by adopting 300W ultrasonic waves, dropwise adding 1 part by weight of ammonia water solution to adjust the pH value of the mixed solution to 8.5, heating to 30 ℃, and stirring for 0.5 hour at the rotating speed of 100 r/min;
step (2): and adding 2 parts by weight of ammonium persulfate solution, dropwise adding into the mixed solution at the speed of 0.01 part by weight/minute, stirring for 2 hours after the dropwise adding is finished, then carrying out suction filtration, and carrying out vacuum drying at 100 ℃ to obtain the ammonium persulfate/sodium persulfate composite material.
Example 2
The anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of the following substances in parts by weight:
100 parts of natural rubber;
50 parts of styrene butadiene rubber;
4 parts of an accelerant;
0.5 part of antioxidant;
4.5 parts of an active agent;
10 parts of sulfur;
20 parts of modified zirconia;
10 parts of activated sepiolite.
The preparation method of the modified zirconia comprises the following steps:
the method comprises the following steps: mixing 100 parts by weight of ethanol, 800 parts by weight of vinyl trimethoxy silane and 100 parts by weight of deionized water, and dropwise adding 10 parts by weight of hydrochloric acid solution to adjust the pH of the mixed solution to 5, wherein the rotating speed is 300 r/m, and the stirring time is 16 hours;
step two: under the protection of nitrogen, 200 parts by weight of zirconia and 20 parts by weight of the mixed solution are added into 2000 parts by weight of toluene solution and stirred at the rotating speed of 300 r/m for 16 hours, modified zirconia is obtained by centrifugal separation, the modified zirconia is cleaned by ethanol solution and dried to constant weight at 70 ℃;
step three: and (2) ultrasonically emulsifying a mixed solution of 100 parts by weight of the modified zirconia, 20 parts by weight of sodium dodecyl sulfate, 30 parts by weight of hexadecanol and 1000 parts by weight of deionized water, carrying out ultrasonic treatment at the ultrasonic frequency of 300kHz and the output power of 300W for 30 minutes, adding 20 parts by weight of ammonium persulfate solution, heating to 80 ℃, dropwise adding 600 parts by weight of the methyl acrylate monomer emulsion into the mixed solution at the speed of 20 parts by weight/minute, carrying out heat preservation for 4 hours after dropwise addition, carrying out suction filtration, and carrying out vacuum drying at the temperature of 100 ℃ to obtain the modified zirconia.
The preparation method of the activated sepiolite comprises the following steps:
step (1): mixing 100 parts by weight of ethanol, 120 parts by weight of polyvinyl alcohol and 2000 parts by weight of deionized water, stirring for 3 hours at the rotating speed of 2800r/min, standing for 18 minutes, treating for 2 minutes by adopting 300W ultrasonic waves, dropwise adding 10 parts by weight of ammonia water solution to adjust the pH value of the mixed solution to 8.5, heating to 50 ℃, and stirring for 1 hour at the rotating speed of 100 r/min;
step (2): and adding 20 parts by weight of ammonium persulfate solution, dropwise adding into the mixed solution at the speed of 20 parts by weight/min, stirring for 2 hours after the dropwise adding is finished, then carrying out suction filtration, and carrying out vacuum drying at 100 ℃ to obtain the ammonium persulfate/sodium persulfate composite material.
Comparative example 1
The anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of the following substances in parts by weight:
100 parts of natural rubber;
50 parts of styrene butadiene rubber;
4 parts of an accelerant;
0.5 part of antioxidant;
4.5 parts of an active agent;
10 parts of sulfur;
10 parts of activated sepiolite.
The preparation method of the activated sepiolite comprises the following steps:
step (1): mixing 100 parts by weight of ethanol, 120 parts by weight of polyvinyl alcohol and 2000 parts by weight of deionized water, stirring for 3 hours at the rotating speed of 2800r/min, standing for 18 minutes, treating for 2 minutes by adopting 300W ultrasonic waves, dropwise adding 1-10 parts by weight of ammonia water solution to adjust the pH value of the mixed solution to 8.5, heating to 50 ℃, and stirring for 1 hour at the rotating speed of 100 r/min;
step (2): and adding 20 parts by weight of ammonium persulfate solution, dropwise adding into the mixed solution at the speed of 20 parts by weight/min, stirring for 2 hours after the dropwise adding is finished, then carrying out suction filtration, and carrying out vacuum drying at 100 ℃ to obtain the ammonium persulfate/sodium persulfate composite material.
Comparative example 2
The anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of the following substances in parts by weight:
100 parts of natural rubber;
50 parts of styrene butadiene rubber;
4 parts of an accelerant;
0.5 part of antioxidant;
4.5 parts of an active agent;
10 parts of sulfur;
20 parts of modified zirconia.
The preparation method of the modified zirconia comprises the following steps:
the method comprises the following steps: mixing 100 parts by weight of ethanol, 800 parts by weight of vinyl trimethoxy silane and 100 parts by weight of deionized water, and dropwise adding 10 parts by weight of hydrochloric acid solution to adjust the pH of the mixed solution to 5, wherein the rotating speed is 300 r/m, and the stirring time is 16 hours;
step two: under the protection of nitrogen, 200 parts by weight of zirconia and 20 parts by weight of the mixed solution are added into 2000 parts by weight of toluene solution and stirred at the rotating speed of 300 r/m for 16 hours, modified zirconia is obtained by centrifugal separation, the modified zirconia is cleaned by ethanol solution and dried to constant weight at 70 ℃;
step three: and (2) ultrasonically emulsifying a mixed solution of 100 parts by weight of the modified zirconia, 20 parts by weight of sodium dodecyl sulfate, 30 parts by weight of hexadecanol and 1000 parts by weight of deionized water, carrying out ultrasonic treatment at the ultrasonic frequency of 300kHz and the output power of 300W for 30 minutes, adding 20 parts by weight of ammonium persulfate solution, heating to 80 ℃, dropwise adding 600 parts by weight of the methyl acrylate monomer emulsion into the mixed solution at the speed of 20 parts by weight/minute, carrying out heat preservation for 4 hours after dropwise addition, carrying out suction filtration, and carrying out vacuum drying at the temperature of 100 ℃ to obtain the modified zirconia.
Comparative example 3
The anti-skidding sole comprises an anti-skidding sole, wherein the anti-skidding sole is composed of the following substances in parts by weight:
100 parts of natural rubber;
50 parts of styrene butadiene rubber;
4 parts of an accelerant;
0.5 part of antioxidant;
4.5 parts of an active agent;
10 parts of sulfur.
The anti-slip shoe soles of examples 1-2 and comparative examples 1-3 were prepared by the following procedure:
step (a): plasticating natural rubber and styrene butadiene rubber on an open mill;
step (b): sequentially adding activated sepiolite, an antioxidant, an active agent and modified zirconia, mixing in an internal mixer, uniformly discharging, wherein the mixing temperature is 78 ℃, and the mixing time is 12 minutes;
step (c): and (c) standing the mixed material obtained in the step (b) for 18 hours, transferring and placing the mixed material into an open mill, adding an accelerator and sulfur, vulcanizing by using a vulcanizing machine, and discharging to obtain a vulcanized rubber sample.
Films prepared in examples 1-2 and comparative examples 1-3 were tested according to SATRA TM144: 2011.
| Coefficient of dry skid resistance | Coefficient of wet slip resistance | |
| Example 1 | 1.31 | 0.90 |
| Example 2 | 1.35 | 0.93 |
| Comparative example 1 | 1.13 | 0.75 |
| Comparative example 2 | 1.03 | 0.85 |
| Comparative example 3 | 1.01 | 0.73 |
The raw rubber in the sole formula of the invention selects natural rubber and styrene-butadiene rubber as main raw materials, wherein the natural rubber is a natural high molecular compound taking polyisoprene as a main component, unsaturated double bonds existing in a molecular structure endow the natural rubber with high chemical reaction capability, excellent mechanical strength and processability are provided, and the sole formula has good elasticity and alkali resistance at normal temperature; the physical and mechanical properties of the styrene butadiene rubber are close to those of natural rubber, and the styrene butadiene rubber also has certain wear resistance and heat resistance and is better in compatibility with other rubbers; an accelerant, an antioxidant, an activator, sulfur and a filler are added into the sole formula, wherein the sulfur is used as a vulcanizing agent to enable rubber macromolecules to be crosslinked into a net structure, and the addition of the accelerant can effectively shorten the reaction rate between the sulfur and the rubber macromolecules and accelerate the crosslinking reaction between the sulfur and the rubber macromolecules; the antioxidant can delay or inhibit the polymer oxidation process, thereby preventing the polymer from aging and prolonging the service life of the polymer, so that the sole material is difficult to oxidize and is more durable; the activator has a synergistic effect with the accelerator, and the presence of the activator can increase the activity of the accelerator, reduce the amount of the accelerator in the reaction system and shorten the time for the vulcanization reaction process to proceed.
As the innovation point of the invention, the filler selects the activated sepiolite and the modified zirconia, and the surface modification treatment is carried out on the zirconia, so that the hydrophilicity of the zirconia is increased, when the sole is rubbed, the hydrophilic zirconia can easily puncture a water film, and the sole can be quickly contacted with a friction surface, so that the wet friction coefficient is increased; the introduction of the activated sepiolite increases the adhesive force between the film and the friction surface, so that the dry friction coefficient mainly based on the adhesive friction force is increased in a dry state; in addition, the modified zirconia is dispersed in the rubber sheet, so that the polarity of the surface of the rubber sheet is increased, and a strong adhesion effect can be generated under the synergistic effect of the modified zirconia and the activated sepiolite, so that the adhesion friction of rubber in contact with a friction surface is increased, and the dry friction coefficient is greatly improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. The utility model provides an enhancement mode antiskid sole and antiskid shoes, includes the antiskid sole, its characterized in that: the anti-skid sole is composed of the following substances in parts by weight:
80-100 parts of natural rubber;
10-50 parts of styrene butadiene rubber;
1-4 parts of an accelerator;
0.1-0.5 part of antioxidant;
2.5-4.5 parts of an active agent;
2-10 parts of sulfur;
6-30 parts of a filler;
the filler is composed of the following substances in parts by weight:
5-20 parts of modified zirconia;
1-10 parts of activated sepiolite.
2. An enhanced anti-slip sole and shoe according to claim 1, wherein: the preparation method of the modified zirconia comprises the following steps:
the method comprises the following steps: mixing 10-100 parts by weight of ethanol, 100-800 parts by weight of silane coupling agent and 10-100 parts by weight of deionized water, dropwise adding 1-10 parts by weight of acid solution to adjust the pH value of the mixed solution to 5, and stirring for 2-16 hours;
step two: under the protection of inert gas, adding 10-200 parts by weight of zirconia and 1-20 parts by weight of the mixed solution into 100-2000 parts by weight of toluene solution, stirring for 2-16 hours, obtaining modified zirconia through centrifugal separation, cleaning the modified zirconia, and drying to constant weight;
step three: emulsifying a mixed solution of 10-100 parts by weight of the modified zirconia, 2-20 parts by weight of sodium dodecyl sulfate, 1-30 parts by weight of hexadecanol and 10-1000 parts by weight of deionized water, adding 2-20 parts by weight of ammonium persulfate solution, heating to 70-80 ℃, dropwise adding 20-600 parts by weight of acrylate monomer emulsion into the mixed solution, preserving heat for 1-4 hours after dropwise adding, performing suction filtration, and performing vacuum drying at 100 ℃ to obtain the acrylic ester monomer emulsion.
3. An enhanced anti-slip sole and shoe according to claim 1, wherein: the preparation method of the activated sepiolite comprises the following steps:
step (1): mixing and stirring 10-100 parts by weight of ethanol, 12-120 parts by weight of polyvinyl alcohol and 200-2000 parts by weight of deionized water for 1-3 hours, dropwise adding 1-10 parts by weight of alkaline solution to adjust the pH value of the mixed solution to 8.5, heating to 30-50 ℃, and stirring for 0.5-1 hour;
step (2): and dropwise adding 2-20 parts by weight of ammonium persulfate solution into the mixed solution, stirring for 2 hours after dropwise adding, performing suction filtration, and performing vacuum drying at 100 ℃ to obtain the ammonium persulfate solution.
4. An enhanced anti-slip sole and shoe according to claim 2, wherein: in the first step, the silane coupling agent is any one of vinyltriethoxysilane, isocyanatopropyltrimethylsilane, aminopropyltriethoxysilane, and vinyltrimethoxysilane.
5. An enhanced anti-slip sole and shoe according to claim 2, wherein: in the first step, the acidic solution is any one of hydrochloric acid, sulfuric acid and phosphoric acid.
6. An enhanced anti-slip sole and shoe according to claim 2, wherein: in the third step, the acrylate monomer is any one or a mixture of more than one of methyl acrylate monomer, ethyl acrylate monomer, methyl methacrylate monomer, hydroxyethyl acrylate monomer and hydroxypropyl acrylate monomer.
7. An enhanced anti-slip sole and shoe according to claim 3, wherein: in the step (1), the alkaline solution is any one of ammonia water, a sodium hydroxide solution and a potassium hydroxide solution.
8. An enhanced anti-slip sole and shoe according to claim 3, wherein: after stirring in step (1), the mixture was allowed to stand for 15 minutes and then treated with 300W ultrasonic waves for 2 minutes.
9. The method for manufacturing the reinforced anti-slip sole and the anti-slip shoe according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step (a): plasticating natural rubber and styrene butadiene rubber on an open mill;
step (b): sequentially adding activated sepiolite, an antioxidant, an active agent and modified zirconia, mixing in an internal mixer, uniformly discharging, wherein the mixing temperature is 75-80 ℃, and the mixing time is 10-12 minutes;
step (c): and (c) standing the mixed material obtained in the step (b) for 15-20 hours, transferring and placing the mixed material in an open mill, adding an accelerator and sulfur, vulcanizing by using a vulcanizing machine, and discharging to obtain a vulcanized rubber sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911006889.3A CN110643084A (en) | 2019-10-22 | 2019-10-22 | Enhancement mode antiskid sole and antiskid shoes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911006889.3A CN110643084A (en) | 2019-10-22 | 2019-10-22 | Enhancement mode antiskid sole and antiskid shoes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110643084A true CN110643084A (en) | 2020-01-03 |
Family
ID=69013320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911006889.3A Pending CN110643084A (en) | 2019-10-22 | 2019-10-22 | Enhancement mode antiskid sole and antiskid shoes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110643084A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154285A (en) * | 2020-01-16 | 2020-05-15 | 温州市丰盛鞋业有限公司 | Woman boot with wear-resistant sole and preparation method thereof |
| CN114292455A (en) * | 2021-12-31 | 2022-04-08 | 浙江恒诚鞋业有限公司 | Rubber sheet for antiskid shoes and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110258886A1 (en) * | 2010-04-26 | 2011-10-27 | Ku Do Moon | Slip-Resistant Rubber Composition, Outsole Using the Rubber Composition and Method of Manufacturing the Outsole |
| KR101165052B1 (en) * | 2010-08-31 | 2012-07-13 | 정재욱 | A composition of non-slip shoe outsole |
| CN105778172A (en) * | 2016-04-11 | 2016-07-20 | 泉州集友鞋业有限公司 | High-anti-slippery abrasion-resistant material for shoes and preparation method thereof |
| CN107090105A (en) * | 2017-06-07 | 2017-08-25 | 界首市盛泽鞋业有限公司 | A kind of anti-skidding sole for children |
-
2019
- 2019-10-22 CN CN201911006889.3A patent/CN110643084A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110258886A1 (en) * | 2010-04-26 | 2011-10-27 | Ku Do Moon | Slip-Resistant Rubber Composition, Outsole Using the Rubber Composition and Method of Manufacturing the Outsole |
| KR101165052B1 (en) * | 2010-08-31 | 2012-07-13 | 정재욱 | A composition of non-slip shoe outsole |
| CN105778172A (en) * | 2016-04-11 | 2016-07-20 | 泉州集友鞋业有限公司 | High-anti-slippery abrasion-resistant material for shoes and preparation method thereof |
| CN107090105A (en) * | 2017-06-07 | 2017-08-25 | 界首市盛泽鞋业有限公司 | A kind of anti-skidding sole for children |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154285A (en) * | 2020-01-16 | 2020-05-15 | 温州市丰盛鞋业有限公司 | Woman boot with wear-resistant sole and preparation method thereof |
| CN114292455A (en) * | 2021-12-31 | 2022-04-08 | 浙江恒诚鞋业有限公司 | Rubber sheet for antiskid shoes and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110713640B (en) | Rubber composition and processing method, and rubber product and production method using same | |
| CN110643084A (en) | Enhancement mode antiskid sole and antiskid shoes | |
| JP3294901B2 (en) | Rubber composition | |
| EP1426409B1 (en) | Rubber composition for tire tread and pneumatic tire using the same | |
| CN110713658B (en) | Rubber composition and processing method, and rubber product and production method using same | |
| JP2004182905A (en) | Rubber composition for tire tread and pneumatic tire produced by using the same | |
| RU2513018C2 (en) | Binding polymer with metal and compounds and compositions suitable for it | |
| JPH0229484A (en) | Material for rubber-coated gasket | |
| JP4571263B2 (en) | Adhesive rubber composition | |
| JP7438210B2 (en) | A silane coupling agent composition comprising a silane compound and a protein modifier, and a rubber composition comprising the same | |
| CN104403118A (en) | Method for improving adhesive performance between nylon canvas and ethylene propylene diene monomer | |
| CN110183708A (en) | A kind of aqueous rubber inorganic agent | |
| US7473472B2 (en) | Adhesive composition for the direct joining of a pre-gelled polyester or vinyl ester to raw rubber | |
| JP6297894B2 (en) | Pneumatic tire | |
| JP5825506B2 (en) | Rubber composition for tire tread | |
| US20230340230A1 (en) | Silane coupling agent composition and rubber composition comprising same | |
| CN114292455B (en) | Rubber sheet for anti-skid shoes and preparation method thereof | |
| CN107459591B (en) | Epoxidized medium-high vinyl polybutadiene rubber and preparation method and application thereof | |
| JP7375775B2 (en) | Method for producing chloroprene graft copolymer latex, adhesive containing the same, and adhesive method | |
| TWI843861B (en) | Silane coupling agent composition containing silane compound and protein modifier, and rubber composition containing the same | |
| CN107619457B (en) | Roof filter cotton treating agent and preparation method thereof | |
| JP2008260863A (en) | Adhesive composition, and method for adhering organic fiber to rubber using the same | |
| JP5650794B2 (en) | Sidewall rubber composition and pneumatic tire | |
| CN106810734B (en) | A kind of transmission belt | |
| JP2514433B2 (en) | Adhesive composition of rubber and fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200103 |
|
| RJ01 | Rejection of invention patent application after publication |