CN115368649A - Anti-skid rubber sole and preparation method thereof - Google Patents
Anti-skid rubber sole and preparation method thereof Download PDFInfo
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- CN115368649A CN115368649A CN202211172839.4A CN202211172839A CN115368649A CN 115368649 A CN115368649 A CN 115368649A CN 202211172839 A CN202211172839 A CN 202211172839A CN 115368649 A CN115368649 A CN 115368649A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 115
- 239000005060 rubber Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 115
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 27
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 27
- 229920005556 chlorobutyl Polymers 0.000 claims abstract description 23
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 21
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 21
- 229920001194 natural rubber Polymers 0.000 claims abstract description 21
- 229920002681 hypalon Polymers 0.000 claims abstract description 20
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 238000003801 milling Methods 0.000 claims abstract 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical class OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 229920000459 Nitrile rubber Polymers 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 12
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 12
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 12
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 12
- YWVDDMRNICWJKM-UHFFFAOYSA-N 11-trimethylsilylundecane-1-thiol Chemical group SCCCCCCCCCCC[Si](C)(C)C YWVDDMRNICWJKM-UHFFFAOYSA-N 0.000 claims description 11
- XOPCHXSYQHXLHJ-UHFFFAOYSA-N 1-(4-aminophenyl)pyrrole-2,5-dione Chemical compound C1=CC(N)=CC=C1N1C(=O)C=CC1=O XOPCHXSYQHXLHJ-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IPNDIMIIGZSERC-UHFFFAOYSA-N 4-(2-sulfanylacetyl)oxybutyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCOC(=O)CS IPNDIMIIGZSERC-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229940071127 thioglycolate Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000126 substance Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 mercapto modified calcium carbonate Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test 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
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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 relates to the technical field of anti-skid soles, in particular to an anti-skid rubber sole and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and open milling natural rubber, butadiene rubber, chlorinated butyl rubber and chlorosulfonated polyethylene rubber; adding calcium carbonate, zinc oxide, zinc stearate, plasticizer dioctyl phthalate, sulfur, accelerator DM and anti-aging agent RD, and banburying; and flat-plate vulcanization is carried out to obtain the rubber sole. According to the invention, through compounding of natural rubber and butadiene rubber and adding chlorinated butyl rubber and chlorosulfonated polyethylene rubber for use, the weather resistance and the processability of the prepared rubber sole are improved, and higher tearing strength and tensile strength are obtained; the anti-slippery performance of the rubber sole is improved by the interaction force among rubber molecular chains and the adhesiveness of halogen atoms; the free volume of a butadiene rubber molecular chain is reduced, the loss factor of the rubber sole is improved, and the wear resistance is improved, so that the comprehensive performance of the prepared rubber shoe material is improved.
Description
Technical Field
The invention relates to the technical field of anti-skid soles, in particular to an anti-skid rubber sole and a preparation method thereof.
Background
With the continuous development of shoe materials, the demand of people on the functionality of sole materials is more and more refined. At present, PU, EVA, rubber and other materials are mostly adopted to make soles in the market, but the PU soles and the EVA soles have poor low-temperature resistance, skid resistance and aging resistance, and rubber is an important strategic material, and as the traditional rubber soles, the PU soles and the EVA soles have excellent wear resistance and water resistance, high-temperature resistance, low-temperature resistance and other environmental adaptability, and higher usage amount. However, the rubber soles have unsatisfactory anti-slip properties and poor anti-slip properties on wet ground. Therefore, the anti-skid rubber sole and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide an anti-skid rubber sole and a preparation method thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: an anti-slip rubber sole comprises the following components in parts by weight: 30 to 40 parts of natural rubber, 60 to 70 parts of butadiene rubber, 15 to 30 parts of chlorinated butyl rubber, 5 to 10 parts of chlorosulfonated polyethylene rubber, 50 to 64 parts of calcium carbonate, 1.2 to 4.5 parts of zinc oxide, 1.6 to 2.0 parts of zinc stearate, 6 to 10 parts of plasticizer dioctyl phthalate, 1.6 to 2.4 parts of sulfur, 1.0 to 1.6 parts of accelerator DM and 1.0 to 1.6 parts of anti-aging agent RD.
Further, natural Rubber (NR): from Xishuangbanna Jingyang rubber, inc.;
butadiene Rubber (BR): 9000 from petrochemicals, qilu petrochemical corporation, china;
chlorinated butyl rubber (CIIR): 1240 from langson chemical industry ltd, germany;
chlorosulfonated polyethylene rubber (CSM): 40, from Jiangxi rainbow chemical Co., ltd;
zinc oxide: the nano zinc oxide is from Jiangsu Wanxiang Zinc industry Co Ltd;
zinc stearate: industrial grade, from the Hangzhou Donghao chemical Co., ltd;
the plasticizer dioctyl phthalate (DEHP): industrial grade, national kingdom chemical ltd;
sulfur: s-80, available from Lin-Yijin SULFONARY GmbH;
accelerator DM: from Shijiazhuang, jubai Guangshi chemical technology Co., ltd;
anti-aging agent RD: from Shandong Youso chemical technology, inc.
Further, the calcium carbonate is subjected to organic surface modification, and the modified calcium carbonate is prepared from the following components: mercapto-modified calcium carbonate, nitrile rubber, 1, 4-butanediol bis (mercaptoacetate) and cardanol derivatives.
Further, the sulfydryl modified calcium carbonate is 11-sulfydryl undecyl trimethyl silane coupling modified calcium carbonate;
calcium carbonate: NAK-2108 from Asahon powder materials, inc. of Quanzhou city;
nitrile Butadiene Rubber (NBR): n3360, available from Ningbo cis rubber, inc.;
in the technical scheme, the natural rubber has the characteristics of good tear resistance, large elasticity, excellent processing performance and the like, but the wear resistance is poorer; the cis-butadiene rubber (cis-1, 4-polybutadiene rubber) has the advantages of high elasticity, good wear resistance, good cold resistance and the like, and is low in heat generation under dynamic load, good in bending resistance and dynamic performance, and the cis-butadiene rubber and the butadiene rubber are blended to be suitable for being used as a sole rubber material. However, natural rubber and butadiene rubber have poor resistance to wet and slippery, low tensile strength and high cold flow property; therefore, the chlorinated butyl rubber and the chlorosulfonated polyethylene rubber are added for use, so that the weather resistance and the processability of the prepared rubber sole can be improved, higher tearing strength and tensile strength are obtained, the stress at definite elongation and the hardness are higher, and the compression permanent deformation is reduced. The brominated butyl rubber has a saturated isobutylene main chain and allyl bromide functional groups, increases the types of crosslinking points, and has excellent co-vulcanization performance with the butadiene rubber.
The chlorinated butyl rubber and the chlorosulfonated polyethylene rubber have higher polarity and large molecular chain internal resistance, so that the interaction force among rubber molecular chains is improved; the adhesiveness of the halogen atoms improves the viscous modulus of the rubber sole, and improves the wet skid resistance of the prepared rubber shoe material; the chlorinated butyl rubber and the chlorosulfonated polyethylene rubber can reduce the free volume of a butadiene rubber molecular chain, increase the friction among materials, enhance the hysteresis, improve the loss factor of the rubber sole, improve the wear resistance of the rubber sole, and improve the comprehensive performance of the prepared rubber sole.
A preparation method of an anti-skid rubber sole comprises the following processes:
placing natural rubber, butadiene rubber, chlorinated butyl rubber and chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 108-115 ℃, and processing for 8-12 min;
adding calcium carbonate, zinc oxide, zinc stearate, plasticizer dioctyl phthalate, sulfur, accelerator DM and anti-aging agent RD, and banburying at 125-135 deg.C for 3-5 min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; unloading, tabletting, stacking the slices after cooling, and standing for 8-24 h; putting the mixture on a flat vulcanizing machine, and vulcanizing the mixture for 10 to 15min at the temperature of between 165 and 175 ℃ and under the pressure of between 10 and 30MPa to obtain the rubber sole.
Further, the calcium carbonate is subjected to organic surface modification, and the method specifically comprises the following steps:
(1) Adding 11-mercapto-undecyltrimethylsilane and calcium carbonate into absolute ethyl alcohol, heating to 65-70 ℃ under the protection of nitrogen atmosphere, stirring, refluxing and reacting for 5-8 h, filtering, extracting with ethanol for 24h, and drying to obtain mercapto-modified calcium carbonate;
the mass ratio of the 11-mercapto-undecyl trimethylsilane to the calcium carbonate is (0.5-1.0): 100;
in the technical scheme, a silicon-oxygen bond in the 11-mercapto-undecyltrimethylsilane reacts with a hydroxyl group on the surface of calcium carbonate for grafting, so that a long-chain quaternary ammonium salt is introduced to the surface of the calcium carbonate to obtain a modified product, the surface hydroxyl group of the calcium carbonate can be eliminated, the agglomeration is reduced, the dispersibility of the calcium carbonate in rubber is improved, a stress concentration point in a prepared shoe material is avoided, and the mechanical property of the sole rubber material after vulcanization is enhanced; the adsorption to auxiliaries and the like can be reduced, and the extension of vulcanization is prevented; improve the interface between the calcium carbonate filler and the rubber, and is beneficial to exerting the synergistic effect.
(2) Taking chloroform, sequentially adding N- (4-aminophenyl) maleimide and paraformaldehyde for dissolving, slowly adding cardanol, heating to 90-95 ℃, and carrying out reflux reaction for 18-22 h; cooling to room temperature, washing with sodium hydroxide aqueous solution and deionized water until the pH is neutral, and removing the solvent by rotary evaporation to obtain a cardanol derivative;
the molar ratio of N- (4-aminophenyl) maleimide to paraformaldehyde to cardanol is 1;
cardanol: derived from yalandt biomaterials, inc, tengzhou;
paraformaldehyde: from Shanghai Aladdin.
(3) Placing nitrile rubber and sulfydryl modified calcium carbonate into a double-roller open mill for plastication for 20-30 min;
adding 1, 4-butanediol bis (thioglycolate) and an initiator Azobisisobutyronitrile (AIBN), heating to 100 ℃, and reacting for 50-75 min;
adding cardanol derivative, continuing to react for 30-60 min, and extruding and granulating to obtain modified calcium carbonate;
further, the modified calcium carbonate comprises the following components in parts by weight: 50-80 parts of nitrile rubber, 60 parts of mercapto modified calcium carbonate, 3.0-4.8 parts of 1, 4-butanediol bis (mercaptoacetate), 0.25-0.56 part of initiator and 4.1-6.7 parts of cardanol derivative.
In the technical scheme, bromine radicals in the modified product react with double bonds in the nitrile rubber to generate electrophilic addition, and the nitrile rubber is introduced and loaded on the surface of calcium carbonate; and then, carrying out click reaction on sulfydryl in 1, 4-butanediol bis (thioglycolate) under the action of an initiator Azobisisobutyronitrile (AIBN), introducing a cardanol derivative, realizing chemical bonding, improving the processability of the prepared modified calcium carbonate, internally plasticizing the nitrile rubber and avoiding the migration of a plasticizer.
After the calcium carbonate subjected to organic surface modification is added into a shoe material, unsaturated groups in the cardanol derivatives can participate in vulcanization in rubber, and can react with olefin bonds in the rubber more easily under the action of zinc oxide to form a heat-resistant cross-linked network structure, so that the cross-linking density is improved, and the vulcanization degree is increased; the calcium carbonate particles are connected through organic matters, and chemical bonding with rubber materials is established to form a strong interface effect, so that the reinforcing effect of the calcium carbonate on the rubber soles is improved, and the wear resistance of shoe materials is enhanced; the prepared modified calcium carbonate has high polarity while improving the dispersibility, and can effectively improve the wet skid resistance of the prepared shoe material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the anti-skid rubber sole and the preparation method thereof, natural rubber and butadiene rubber are compounded to serve as a base rubber material of the sole, so that the anti-skid rubber sole has good elasticity, tear resistance, wear resistance and other properties; and adding chlorinated butyl rubber and chlorosulfonated polyethylene rubber for use, improving the weather resistance and the processability of the prepared rubber sole, obtaining higher tearing strength and tensile strength, and reducing the compression permanent deformation, and the stress at definite elongation and the hardness are higher; the anti-slippery performance of the rubber sole is improved by the interaction force among rubber molecular chains and the adhesiveness of halogen atoms; the free volume of a butadiene rubber molecular chain is reduced, the loss factor of the rubber sole is improved, and the wear resistance is improved, so that the comprehensive performance of the prepared rubber shoe material is improved.
2. According to the anti-skid rubber sole and the preparation method thereof, the calcium carbonate is modified by the nitrile rubber and the cardanol derivative, so that the dispersibility between calcium carbonate particles and rubber materials is improved, the nitrile rubber is internally plasticized, the polarity is high, and the anti-skid capability of the prepared shoe material is effectively improved; after the calcium carbonate is added into shoe materials, a network cross-linking structure is formed through reaction, calcium carbonate particles are connected through organic matters, chemical combination with a sole sizing material is established, a strong interface effect is formed, the reinforcing effect of the calcium carbonate on rubber soles is favorably improved, and the wear resistance of the shoe materials is enhanced.
3. According to the anti-skid rubber sole and the preparation method thereof, the cardanol derivative with oxazine rings is generated through the reaction of N- (4-aminophenyl) maleimide, paraformaldehyde and cardanol, olefin in unsaturated long chain and maleimide reacts with unsaturated olefin in nitrile rubber, chlorinated butyl rubber and the like, the cross-linking property of the prepared sole sizing material is improved, the oxazine ring structure is introduced, ring-opening curing is carried out under the action of heat, the sole sizing material is toughened, the thermal stability is improved, and the comprehensive mechanical property of the prepared rubber sole is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing modified calcium carbonate:
1.1. adding 0.5 part by mass of 11-mercaptoundecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 65 ℃ under the protection of nitrogen atmosphere, stirring, refluxing, reacting for 5 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain mercapto-modified calcium carbonate;
1.2. taking 100 parts by mass of chloroform, sequentially adding 23.5 parts by mass of N- (4-aminophenyl) maleimide and 4.95 parts by mass of paraformaldehyde for dissolving, slowly adding 25 parts by mass of cardanol, heating to 90 ℃, and carrying out reflux reaction for 18 hours; cooling to room temperature, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with water until the pH value is neutral, and performing rotary evaporation to remove the solvent to obtain a cardanol derivative;
1.3. 150 parts by mass of nitrile rubber and 180 parts by mass of mercapto modified calcium carbonate are placed in a double-roll open mill for plastication for 20min;
adding 9.0 parts by mass of 1, 4-butanediol bis (mercaptoacetate) and 0.75 part by mass of initiator azobisisobutyronitrile, heating to 100 ℃, and reacting for 50min;
adding 12.3 parts by mass of cardanol derivatives, continuously reacting for 30min, and extruding and granulating to obtain modified calcium carbonate;
(2) Preparing a rubber sole:
placing 300 parts by mass of natural rubber, 600 parts by mass of butadiene rubber, 150 parts by mass of chlorinated butyl rubber and 50 parts by mass of chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 108 ℃, and processing for 8min;
adding 500 parts by mass of modified calcium carbonate, 12 parts by mass of zinc oxide, 16 parts by mass of zinc stearate, 60 parts by mass of plasticizer dioctyl phthalate, 16 parts by mass of sulfur, 10 parts by mass of accelerator DM and 10 parts by mass of anti-aging agent RD, and banburying at 125 ℃ for 3min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 8 hours; placing on a flat vulcanizing machine, vulcanizing at 165 deg.C and 20MPa for 10min to obtain the rubber sole.
Example 2
(1) Preparing modified calcium carbonate:
1.1. adding 0.8 part by mass of 11-mercapto-undecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 68 ℃ under the protection of nitrogen atmosphere, stirring, refluxing for 6 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain mercapto-modified calcium carbonate;
1.2. taking 100 parts by mass of chloroform, sequentially adding 23.5 parts by mass of N- (4-aminophenyl) maleimide and 4.95 parts by mass of paraformaldehyde for dissolving, slowly adding 25 parts by mass of cardanol, heating to 92 ℃, and carrying out reflux reaction for 20 hours; cooling to room temperature, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with water until the pH is neutral, and removing the solvent by rotary evaporation to obtain cardanol derivatives;
1.3. placing 195 parts by mass of nitrile rubber and 180 parts by mass of sulfydryl modified calcium carbonate in a double-roller open mill for plastication for 25min;
adding 11.7 parts by mass of 1, 4-butanediol bis (mercaptoacetate) and 1.20 parts by mass of initiator azobisisobutyronitrile, heating to 100 ℃, and reacting for 62min;
adding 16.2 parts by mass of cardanol derivative, continuously reacting for 45min, and extruding and granulating to obtain modified calcium carbonate;
(2) Preparing a rubber sole:
placing 350 parts by mass of natural rubber, 650 parts by mass of cis-butadiene rubber, 220 parts by mass of chlorinated butyl rubber and 80 parts by mass of chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 110 ℃, and processing for 10min;
adding 570 parts by mass of modified calcium carbonate, 28 parts by mass of zinc oxide, 18 parts by mass of zinc stearate, 80 parts by mass of plasticizer dioctyl phthalate, 20 parts by mass of sulfur, 13 parts by mass of accelerator DM and 13 parts by mass of anti-aging agent RD, and banburying at the temperature of 130 ℃ for 4min;
after mixing uniformly, orienting for many times, and discharging pieces to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 16h; placing on a flat vulcanizing machine, vulcanizing at 170 deg.C and 20MPa for 12min to obtain the rubber sole.
Example 3
(1) Preparing modified calcium carbonate:
1.1. adding 1.0 part by mass of 11-mercapto-undecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 70 ℃ under the protection of nitrogen atmosphere, stirring, refluxing for 8 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain mercapto-modified calcium carbonate;
1.2. taking 100 parts by mass of chloroform, sequentially adding 23.5 parts by mass of N- (4-aminophenyl) maleimide and 4.95 parts by mass of paraformaldehyde for dissolving, slowly adding 25 parts by mass of cardanol, heating to 95 ℃, and carrying out reflux reaction for 22 hours; cooling to room temperature, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with water until the pH value is neutral, and performing rotary evaporation to remove the solvent to obtain a cardanol derivative;
1.3. placing 240 parts by mass of nitrile rubber and 180 parts by mass of sulfydryl modified calcium carbonate in a double-roller open mill for plastication for 30min;
adding 14.4 parts by mass of 1, 4-butanediol bis (mercaptoacetate) and 1.68 parts by mass of initiator azobisisobutyronitrile, heating to 100 ℃, and reacting for 75min;
adding 20.1 parts by mass of cardanol derivative, continuously reacting for 60min, and extruding and granulating to obtain modified calcium carbonate;
(2) Preparing a rubber sole:
placing 400 parts by mass of natural rubber, 700 parts by mass of butadiene rubber, 300 parts by mass of chlorinated butyl rubber and 100 parts by mass of chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the roller temperature of the open mill to be 115 ℃, and processing for 12min;
adding 640 parts by mass of modified calcium carbonate, 45 parts by mass of zinc oxide, 20 parts by mass of zinc stearate, 100 parts by mass of plasticizer dioctyl phthalate, 24 parts by mass of sulfur, 16 parts by mass of accelerator DM and 16 parts by mass of anti-aging agent RD, and banburying at the temperature of 135 ℃ for 5min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 24h; placing on a flat vulcanizing machine, vulcanizing at 175 deg.C and 30MPa for 15min to obtain the rubber sole.
Comparative example 1
(1) Preparing modified calcium carbonate:
1.1. adding 0.5 part by mass of 11-mercapto-undecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 65 ℃ under the protection of nitrogen atmosphere, stirring, refluxing for 5 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain mercapto-modified calcium carbonate;
1.2. taking 100 parts by mass of chloroform, sequentially adding 23.5 parts by mass of N- (4-aminophenyl) maleimide and 4.95 parts by mass of paraformaldehyde for dissolving, slowly adding 25 parts by mass of cardanol, and heating to 90 ℃ for reflux reaction for 18 hours; cooling to room temperature, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with water until the pH value is neutral, and performing rotary evaporation to remove the solvent to obtain a cardanol derivative;
1.3. placing 150 parts by mass of nitrile rubber and 180 parts by mass of sulfydryl modified calcium carbonate in a double-roll open mill for plastication for 20min;
adding 9.0 parts by mass of 1, 4-butanediol bis (thioglycolic acid ester) and 0.75 part by mass of initiator azobisisobutyronitrile, heating to 100 ℃, reacting for 50min, and extruding and granulating to obtain modified calcium carbonate;
and (3) obtaining the rubber sole in the same way as the example 1 in the step (2).
Comparative example 2
(1) Preparing modified calcium carbonate:
1.1. adding 0.5 part by mass of 11-mercapto-undecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 65 ℃ under the protection of nitrogen atmosphere, stirring, refluxing for 5 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain mercapto-modified calcium carbonate;
1.2. taking 100 parts by mass of chloroform, sequentially adding 23.5 parts by mass of N- (4-aminophenyl) maleimide and 4.95 parts by mass of paraformaldehyde for dissolving, slowly adding 25 parts by mass of cardanol, and heating to 90 ℃ for reflux reaction for 18 hours; cooling to room temperature, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with water until the pH value is neutral, and performing rotary evaporation to remove the solvent to obtain a cardanol derivative;
1.3. taking 500 parts by mass of toluene and 180 parts by mass of mercapto-modified calcium carbonate, adding 12.3 parts by mass of cardanol derivative and 0.75 part by mass of initiator azobisisobutyronitrile, heating to 100 ℃, and reacting for 50min; filtering and drying to obtain modified calcium carbonate;
(2) Preparing a rubber sole:
placing 300 parts by mass of natural rubber, 600 parts by mass of butadiene rubber, 150 parts by mass of chlorinated butyl rubber and 50 parts by mass of chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 108 ℃, and processing for 8min;
adding 272 parts by mass of modified calcium carbonate, 12 parts by mass of zinc oxide, 16 parts by mass of zinc stearate, 60 parts by mass of plasticizer dioctyl phthalate, 16 parts by mass of sulfur, 10 parts by mass of accelerator DM and 10 parts by mass of anti-aging agent RD, and banburying at 125 ℃ for 3min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 8 hours; placing on a flat vulcanizing machine, vulcanizing at 165 deg.C and 20MPa for 10min to obtain the rubber sole.
Comparative example 3
(1) Preparing modified calcium carbonate:
adding 1.0 part by mass of 11-mercapto-undecyltrimethylsilane and 100 parts by mass of calcium carbonate into 300 parts by mass of absolute ethanol, heating to 70 ℃ under the protection of nitrogen atmosphere, stirring, refluxing for 8 hours, filtering, extracting with ethanol for 24 hours, and drying to obtain modified calcium carbonate;
(2) Preparing a rubber sole:
placing 300 parts by mass of natural rubber, 600 parts by mass of butadiene rubber, 150 parts by mass of chlorinated butyl rubber and 50 parts by mass of chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 108 ℃, and processing for 8min;
adding 255 parts by mass of modified calcium carbonate, 12 parts by mass of zinc oxide, 16 parts by mass of zinc stearate, 60 parts by mass of plasticizer dioctyl phthalate, 16 parts by mass of sulfur, 10 parts by mass of accelerator DM and 10 parts by mass of anti-aging agent RD, and banburying at 125 ℃ for 3min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 8 hours; placing on a flat vulcanizing machine, vulcanizing at 165 deg.C and 20MPa for 10min to obtain the rubber sole.
Comparative example 4
(2) Preparing a rubber sole:
placing 320 parts by mass of natural rubber, 630 parts by mass of butadiene rubber and 150 parts by mass of chlorinated butyl rubber into a double-roller open mill, controlling the temperature of a roller of the open mill to be 108 ℃, and processing for 8min;
adding 500 parts by mass of modified calcium carbonate, 12 parts by mass of zinc oxide, 16 parts by mass of zinc stearate, 60 parts by mass of plasticizer dioctyl phthalate, 16 parts by mass of sulfur, 10 parts by mass of accelerator DM and 10 parts by mass of anti-aging agent RD, and banburying at 125 ℃ for 3min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 8 hours; placing on a flat vulcanizing machine, vulcanizing at 165 deg.C and 20MPa for 10min to obtain the rubber sole.
Step (1) was the same as in comparative example 3.
Comparative example 5
(2) Preparing a rubber sole:
placing 400 parts by mass of natural rubber and 700 parts by mass of butadiene rubber into a double-roller open mill, controlling the temperature of a roller of the open mill to be 108 ℃, and processing for 8min;
adding 500 parts by mass of modified calcium carbonate, 12 parts by mass of zinc oxide, 16 parts by mass of zinc stearate, 60 parts by mass of plasticizer dioctyl phthalate, 16 parts by mass of sulfur, 10 parts by mass of accelerator DM and 10 parts by mass of anti-aging agent RD, and banburying at 125 ℃ for 3min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; discharging, tabletting, cooling, stacking the slices, and standing for 8 hours; placing on a flat vulcanizing machine, vulcanizing at 165 deg.C and 20MPa for 10min to obtain the rubber sole.
Step (1) was the same as in comparative example 3.
The above examples and comparative examples are all laboratory pilot scale processes, wherein "1 part by mass" is represented as 1g, and the amounts of raw materials used in the preparation methods can be scaled up in equal proportions.
Natural Rubber (NR): from Xishuangbanna Jingyang rubber, inc.;
butadiene Rubber (BR): 9000 from petrochemicals, qilu petrochemical corporation, china;
chlorinated butyl rubber (CIIR): 1240, from langson chemical industry ltd, germany;
chlorosulfonated polyethylene rubber (CSM): 40, from Jiangxi rainbow chemical Co., ltd;
zinc oxide: the nano zinc oxide is from Jiangsu Wanxiang Zinc industry Co Ltd;
zinc stearate: industrial grade, from the Hangzhou Donghao chemical Co., ltd;
the plasticizer dioctyl phthalate (DEHP): industrial grade, golden spring chemical limited, xiongcounty;
sulfur: s-80, available from Lin-Yijin SULFONARY GmbH;
accelerator DM: from Shijiazhuang, jubai Guangshi chemical technology Co., ltd;
anti-aging agent RD: from Shandong Youso chemical technology, inc.;
calcium carbonate: NAK-2108 from Asahon powder materials Limited, quanzhou;
nitrile Butadiene Rubber (NBR): n3360, available from Ningbo cis rubber, inc.;
cardanol: derived from yalandte biomaterials, inc, tengzhou;
paraformaldehyde: from Shanghai Aladdin.
Experiment of the invention
Taking the rubber soles obtained in the examples 1-3 and the comparative examples 1-5 to prepare samples, respectively detecting the performances of the samples and recording the detection results:
mechanical property test: testing the tensile property and the tearing property of the sample by adopting an electronic tensile testing machine by taking GB/T528-2009 and GB/T529-2008 as reference standards; the sample size is 100mm multiplied by 5.0mm multiplied by 2.0mm, and the stretching speed is 500mm/min;
anti-skid performance test: testing the dry method/wet method slip resistance of a sample by taking HG/T3780-2005 as a reference standard of an experiment, wherein water is selected as a wet method medium; the sample is square, and the size is 76mm multiplied by 76mm;
wear resistance test: taking a rotary roller type abrasion method in GB/T9867-2009 as a reference standard, testing the abrasion resistance of a sample, wherein the sample is cylindrical and has the size of 16mm multiplied by 10mm;
from the data in the table above, it is clear that the following conclusions can be drawn:
the rubber soles obtained in examples 1 to 3 were compared with those obtained in comparative examples 1 to 5, and the results of the measurements were confirmed,
compared with the comparative example, the rubber soles obtained in the examples 1 to 3 have higher tensile strength, tear strength and skid resistance data and lower wear resistance experimental data, which fully shows that the application realizes the improvement of the mechanical property, skid resistance and wear resistance of the prepared rubber soles.
In comparison with example 1, cardanol derivative, which is not a component, was not added in comparative example 1; in comparative example 2, nitrile rubber was not added as a component; in comparative example 3, mercapto-modified calcium carbonate was taken as modified calcium carbonate; on the basis of comparative example 3 in comparative example 4, chlorosulfonated polyethylene rubber was not added as a component; on the basis of comparative example 4 in comparative example 5, chlorinated butyl rubber and chlorosulfonated polyethylene rubber were not added as components; the rubber soles obtained in comparative examples 1 to 5 had reduced tensile strength, tear strength and grip performance data and increased wear resistance test data; the prepared rubber sole component and the process thereof can promote the comprehensive improvement of the mechanical property, the anti-skid property, the wear resistance and the like.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an anti-skid rubber sole is characterized by comprising the following steps: the method comprises the following processes:
mixing and open-milling natural rubber, butadiene rubber, chlorinated butyl rubber and chlorosulfonated polyethylene rubber; adding calcium carbonate, zinc oxide, zinc stearate, plasticizer dioctyl phthalate, sulfur, accelerator DM and anti-aging agent RD, and banburying; and flat-plate vulcanization is carried out to obtain the rubber sole.
2. The method for preparing an anti-slip rubber sole according to claim 1, wherein the method comprises the following steps: the method comprises the following processes:
placing natural rubber, butadiene rubber, chlorinated butyl rubber and chlorosulfonated polyethylene rubber in a double-roller open mill, controlling the temperature of a roller of the open mill to be 108-115 ℃, and processing for 8-12 min;
adding calcium carbonate, zinc oxide, zinc stearate, plasticizer dioctyl phthalate, sulfur, accelerator DM and anti-aging agent RD, and banburying at 125-135 deg.C for 3-5 min;
after mixing uniformly, orienting for many times, and discharging to obtain mixed rubber; unloading, tabletting, stacking the slices after cooling, and standing for 8-24 h; putting the mixture on a flat vulcanizing machine, vulcanizing the mixture for 10 to 15min at the temperature of between 165 and 175 ℃ and under the pressure of between 10 and 30MPa to obtain the rubber sole.
3. The method for preparing an anti-slip rubber sole according to claim 1, characterized in that: the rubber sole comprises the following components in parts by weight: 30 to 40 parts of natural rubber, 60 to 70 parts of butadiene rubber, 15 to 30 parts of chlorinated butyl rubber, 5 to 10 parts of chlorosulfonated polyethylene rubber, 50 to 64 parts of calcium carbonate, 1.2 to 4.5 parts of zinc oxide, 1.6 to 2.0 parts of zinc stearate, 6 to 10 parts of plasticizer dioctyl phthalate, 1.6 to 2.4 parts of sulfur, 1.0 to 1.6 parts of accelerator DM and 1.0 to 1.6 parts of anti-aging agent RD.
4. The method for preparing an anti-slip rubber sole according to claim 1, wherein the method comprises the following steps: the calcium carbonate is subjected to organic surface modification, and the modified calcium carbonate is prepared from the following components: mercapto-modified calcium carbonate, nitrile rubber, 1, 4-butanediol bis (mercaptoacetate) and cardanol derivatives.
5. The method for preparing an anti-slip rubber sole according to claim 4, wherein the method comprises the following steps: the mercapto-modified calcium carbonate is 11-mercapto-undecyl trimethyl silane coupling modified calcium carbonate.
6. The method for preparing an anti-slip rubber sole according to claim 4, wherein the method comprises the following steps: the modified calcium carbonate is prepared by the following process:
placing nitrile rubber and sulfydryl modified calcium carbonate into a double-roller open mill for plastication for 20-30 min;
adding 1, 4-butanediol bis (mercaptoacetate) and an initiator azobisisobutyronitrile, heating to 100 ℃, and reacting for 50-75 min;
adding cardanol derivative, continuing to react for 30-60 min, and extruding and granulating to obtain the modified calcium carbonate.
7. The method for preparing an anti-slip rubber sole according to claim 6, wherein the method comprises the following steps: the modified calcium carbonate comprises the following components in parts by weight: 50-80 parts of nitrile rubber, 60 parts of sulfydryl modified calcium carbonate, 3.0-4.8 parts of 1, 4-butanediol bis (thioglycolate), 0.25-0.56 part of initiator and 4.1-6.7 parts of cardanol derivative.
8. The method for preparing an anti-slip rubber sole according to claim 5, wherein the method comprises the following steps: the cardanol derivative is prepared by the following process:
and (3) taking chloroform, sequentially adding N- (4-aminophenyl) maleimide and paraformaldehyde for dissolving, slowly adding cardanol, heating to 90-95 ℃, and carrying out reflux reaction for 18-22 h to obtain the cardanol derivative.
9. The method for preparing an anti-slip rubber sole according to claim 8, wherein the method comprises the following steps: the molar ratio of the N- (4-aminophenyl) maleimide to the paraformaldehyde to the cardanol is 1.
10. An anti-slip rubber shoe sole produced by the production method according to any one of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
| CN104356441A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Wear-resistant antistatic rubber shoe sole and preparation method thereof |
| CN109134959A (en) * | 2018-08-06 | 2019-01-04 | 广州维桢化工科技有限公司 | A kind of foaming sole material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
| CN104356441A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Wear-resistant antistatic rubber shoe sole and preparation method thereof |
| CN109134959A (en) * | 2018-08-06 | 2019-01-04 | 广州维桢化工科技有限公司 | A kind of foaming sole material and preparation method thereof |
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