CN117050405B - High-strength sole adhesive and production process thereof - Google Patents
High-strength sole adhesive and production process thereof Download PDFInfo
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- CN117050405B CN117050405B CN202311261485.5A CN202311261485A CN117050405B CN 117050405 B CN117050405 B CN 117050405B CN 202311261485 A CN202311261485 A CN 202311261485A CN 117050405 B CN117050405 B CN 117050405B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000853 adhesive Substances 0.000 title claims description 22
- 230000001070 adhesive effect Effects 0.000 title claims description 22
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 63
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 45
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 45
- 229920001194 natural rubber Polymers 0.000 claims abstract description 45
- 239000006229 carbon black Substances 0.000 claims abstract description 38
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 24
- 239000005060 rubber Substances 0.000 claims abstract description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 230000008878 coupling Effects 0.000 claims abstract description 11
- 238000010168 coupling process Methods 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical group CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000007598 dipping method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 12
- 239000004816 latex Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical compound CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 claims description 5
- VWIQHHBCAQFZCF-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.Cl Chemical compound C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.Cl VWIQHHBCAQFZCF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920006173 natural rubber latex Polymers 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000032683 aging Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process 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
- C08L9/06—Copolymers with styrene
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of rubber materials, and discloses high-strength sole rubber and a production process thereof, wherein the high-strength sole rubber comprises the following components in parts by weight: 30-40 parts of modified natural rubber, 50-70 parts of styrene-butadiene rubber, 20-30 parts of nitrile rubber, 10-15 parts of composite filler, 5-10 parts of modified aramid fiber, 0.1-0.5 part of anti-aging agent, 0.1-0.5 part of accelerator and 1-3 parts of sulfur; the modified natural rubber is diacetone acrylamide grafted modified natural rubber; the composite filler is an anti-aging coupling agent-GO-white carbon black composite material, and the anti-aging coupling agent is p-phenylenediamine grafted gamma-urea propyl triethoxysilane; the high-strength sole rubber disclosed by the invention adopts the styrene-butadiene rubber and the nitrile rubber to reinforce the modified natural rubber, and meanwhile, the composite filler and the modified aramid fiber are added, so that the mechanical property and the ageing resistance of the high-strength sole rubber are greatly improved.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to high-strength sole rubber and a production process thereof.
Background
The construction of the sole is quite complex and, in a broad sense, may include all of the materials comprising the sole, midsole, heel, etc. In a narrow sense, the sole material should have the common characteristics of wear resistance, water resistance, oil resistance, heat resistance, pressure resistance, impact resistance, good elasticity, easy adaptation to the foot, difficult deformation after shaping, heat preservation, easy absorption of moisture and the like, and the sole should be matched with the midsole, so that the sole material has various conditions of braking action, no slipping, easy stopping and the like when walking for changing feet.
The sole is made of EVA, TPR, PU, PVC, rubber and other materials. According to the current research situation of the rubber shoe industry, polyvinyl chloride or natural rubber is mainly used as a main material for manufacturing the shoe body. Because polyvinyl chloride and natural rubber both have cold hardness, under the condition of lower temperature, the sole made of the polyvinyl chloride or the natural rubber is extremely easy to be hardened, the strength and the flexibility are seriously reduced, and even the sole is broken. Therefore, adding auxiliary agents, modifying or compounding and collocating become the direction for developing novel shoe materials.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide the high-strength sole rubber and the production process thereof, wherein the styrene-butadiene rubber and the nitrile rubber are adopted to reinforce the modified natural rubber, and meanwhile, the composite filler and the modified aramid fiber are added, so that the mechanical property and the ageing resistance of the high-strength sole rubber are greatly improved.
The aim of the invention can be achieved by the following technical scheme:
the high-strength sole adhesive comprises the following components in parts by weight: 30-40 parts of modified natural rubber, 50-70 parts of styrene-butadiene rubber, 20-30 parts of nitrile rubber, 10-15 parts of composite filler, 5-10 parts of modified aramid fiber, 0.1-0.5 part of anti-aging agent, 0.1-0.5 part of accelerator and 1-3 parts of sulfur;
the modified natural rubber is diacetone acrylamide grafted modified natural rubber;
the composite filler is an anti-aging coupling agent-GO-white carbon black composite material, and the anti-aging coupling agent is p-phenylenediamine grafted gamma-urea propyl triethoxysilane;
the modified aramid fiber is obtained by treating aramid nanofiber with caprolactam-blocked isocyanate and then dipping RFL (rfL) dipping solution, wherein the RFL dipping solution is resorcinol, formaldehyde and butyl-pyridine emulsion.
Further preferably, the anti-aging agent is one or more of an anti-aging agent D, an anti-aging agent AW, an anti-aging agent DNP, an anti-aging agent 4020 and an anti-aging agent 4010NA, and the accelerator is one or more of an accelerator DM, an accelerator M, an accelerator TMTD or an accelerator D.
Further preferably, the method for producing the modified natural rubber comprises the steps of:
(1) Adding natural rubber latex into constant temperature water bath equipment, adding sodium dodecyl benzene sulfonate and ammonia water, and stirring at room temperature for 20-40 min under the protection of nitrogen;
(2) Adding benzoyl peroxide chloride into a reaction system, heating to 50-55 ℃, and slowly adding diacetone acrylamide and triethyl phosphonoacetate for 1-3 hours;
(3) And (3) carrying out heat preservation reaction for 3-5 hours, and carrying out vacuum drying at 70 ℃ to balance weight after the latex is coagulated, so as to obtain the modified natural rubber.
Further preferably, the preparation method of the composite filler comprises the following steps:
A. grafting p-phenylenediamine into coupling agent gamma-urea propyl triethoxysilane to prepare an anti-aging coupling agent;
B. respectively adding graphene oxide and white carbon black into deionized water for ultrasonic dispersion, then mixing a graphene oxide solution and a white carbon black solution, adding ammonia water to adjust the pH value to 8, and continuing ultrasonic treatment for 8-12 hours;
C. adding the ultrasonic graphene oxide and white carbon black mixed solution into a reactor, adding the anti-aging coupling agent prepared in the step A, and stirring at 55-65 ℃ for reaction for 8-12 hours;
D. and after the reaction is finished, carrying out vacuum filtration on the reactant, washing the reactant for 3 to 5 times by using absolute ethyl alcohol and deionized water, and then drying the reactant at 50 to 60 ℃ for 12 to 24 hours to obtain the anti-aging coupling agent-GO-white carbon black composite material.
Further preferably, the chemical reaction equation for the synthesis of the anti-aging coupling agent in step a is as follows:
；
the preparation method specifically comprises the following steps:
a1, weighing p-phenylenediamine, putting the p-phenylenediamine into a flask, adding absolute ethyl alcohol, heating to 60-70 ℃, and stirring at a constant temperature until the p-phenylenediamine is completely dissolved;
and A2, adding gamma-urea propyl triethoxysilane, reacting for 10-12 hours at the constant temperature of 80-85 ℃ in a nitrogen atmosphere, and then cooling to room temperature to obtain the anti-aging coupling agent.
Further preferably, in the step B, graphene oxide and white carbon black are mixed according to a mass ratio of 1:10-20.
Further preferably, the preparation method of the modified aramid fiber comprises the following steps:
i, mixing epoxy resin, caprolactam blocked isocyanate and deionized water in proportion to prepare pretreatment liquid;
adding resorcinol and formaldehyde into deionized water according to a certain proportion, uniformly mixing, reacting for 4-6 hours at normal temperature, adding a certain amount of butadiene-pyridine latex, and stirring for 1-2 hours to obtain RFL (RFL dipping solution);
III, immersing the aramid fiber in the pretreatment liquid for 10-15 s, drying at 150-160 ℃ for 60-90 s, and curing at 220-230 ℃ for 60-90 s. The method comprises the steps of carrying out a first treatment on the surface of the
And IV, dipping the pretreated aramid fiber into RFL dipping solution for 20-30 s, drying at 150-160 ℃ for 60-90 s, and curing at 220-230 ℃ for 60-90 s to obtain the modified aramid fiber.
Further preferably, the mass ratio of epoxy resin, caprolactam blocked isocyanate and deionized water in step I is 1:5:60.
further preferably, the mass ratio of resorcinol, formaldehyde and butadiene-pyridine latex in the step II is 1:1:10.
a production process of high-strength sole glue comprises the following steps: adding the modified natural rubber, the styrene-butadiene rubber and the nitrile rubber into a rubber open mill for molding, adding the composite filler, the modified aramid fiber and the anti-aging agent for mixing for 3-5 min after the molding is uniform, adding the sulfur and the accelerator for mixing uniformly, and vulcanizing for 8-10 min at 140 ℃ to obtain the high-strength sole rubber sheet.
The invention has the beneficial effects that:
the high-strength sole rubber disclosed by the invention adopts the styrene-butadiene rubber and the nitrile rubber to reinforce the modified natural rubber, and meanwhile, the composite filler and the modified aramid fiber are added, so that the mechanical property and the ageing resistance of the high-strength sole rubber are greatly improved. The modified natural rubber is grafted with diacetone acrylamide monomer, and the ketone carbonyl in diacetone acrylamide is utilized to make the polymer undergo the reactions of crosslinking grafting and the like, and the long chains of the natural rubber are connected together to form a crosslinked network by adding a crosslinking agent, so that the mechanical property of the natural rubber is improved.
The invention utilizes p-phenylenediamine and gamma-urea propyl triethoxysilane to react to prepare the silane coupling agent with the anti-aging function, which is not easy to decompose and migrate, solves the problem that the conventional anti-aging agent is easy to volatilize and migrate from materials, and prolongs the anti-aging effect.
According to the invention, the self-made anti-aging coupling agent is adopted to modify graphene oxide and white carbon black simultaneously, ethoxy at one end of the anti-aging coupling agent is hydrolyzed to generate silicon hydroxyl, condensation reaction is carried out on the silicon hydroxyl and the hydroxyl of the white carbon black, the amino on the anti-aging coupling agent can be subjected to amidation reaction with carboxyl functional groups on the surface of the graphene oxide, and the amino is grafted to the surface of the graphene oxide, so that the white carbon black can be firmly fixed between graphene oxide sheets, an isolation effect is achieved, the graphene oxide sheets are in a loose structure, and dispersion in rubber is facilitated.
According to the invention, after the epoxy resin and the blocked isocyanate treatment system are adopted for treatment, the RFL dipping liquid is added for treatment, so that the aggregation of the aramid nanofibers can be prevented, the aramid nanofibers and the rubber can be further bonded, and the mechanical property of the rubber material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
FIG. 1 is an infrared spectrum of the invention before and after modification of the natural rubber in example 3;
FIG. 2 is an SEM photograph of the anti-aging coupling agent-GO-white carbon black of example 6 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the modified natural rubber comprises the following steps:
(1) Adding natural rubber latex into constant temperature water bath equipment, adding sodium dodecyl benzene sulfonate and ammonia water, and stirring at room temperature for 20min under the protection of nitrogen;
(2) Adding benzoyl peroxide chloride into a reaction system, heating to 55 ℃, and slowly adding diacetone acrylamide and triethyl phosphonoacetate for 1h;
(3) And (3) carrying out heat preservation reaction for 5 hours, and carrying out vacuum drying at 70 ℃ to balance weight after the latex is coagulated, so as to obtain the modified natural rubber.
Example 2
The preparation method of the modified natural rubber comprises the following steps:
(1) Adding natural rubber latex into constant temperature water bath equipment, adding sodium dodecyl benzene sulfonate and ammonia water, and stirring at room temperature under the protection of nitrogen for 40min;
(2) Adding benzoyl peroxide chloride into a reaction system, heating to 50 ℃, and slowly adding diacetone acrylamide and triethyl phosphonoacetate for 3 hours;
(3) And (3) carrying out heat preservation reaction for 3 hours, and carrying out vacuum drying at 70 ℃ to balance weight after the latex is coagulated, so as to obtain the modified natural rubber.
Example 3
The preparation method of the modified natural rubber comprises the following steps:
(1) Adding natural rubber latex into constant temperature water bath equipment, adding sodium dodecyl benzene sulfonate and ammonia water, and stirring at room temperature for 30min under the protection of nitrogen;
(2) Adding benzoyl peroxide chloride into a reaction system, heating to 52 ℃, and slowly adding diacetone acrylamide and triethyl phosphonoacetate for 2 hours;
(3) And (3) carrying out heat preservation reaction for 4 hours, and carrying out vacuum drying at 70 ℃ to balance weight after the latex is coagulated, so as to obtain the modified natural rubber.
The results of the infrared spectrum test analysis of the natural rubber and the modified natural rubber in example 3 are shown in FIG. 1, and it can be seen that 2961cm of the modified natural rubber is obtained on the infrared spectrum -1 、2894cm -1 、2846cm -1 The position corresponds to natural rubber-CH 3 and-CH 2 The characteristic absorption peak of (C) still exists, but at 1722cm -1 There appears a characteristic absorption peak of the stretching vibration of carbonyl (C=O), which is not found in the infrared spectrogram of the original natural rubber, and is found at 3196cm -1 There appears a characteristic absorption peak of the stretching vibration of the amine group (NH), so diacetone acrylamide is successfully polymerized with natural rubber.
Example 4
The preparation method of the composite filler comprises the following steps:
A. grafting p-phenylenediamine into coupling agent gamma-urea propyl triethoxysilane to prepare the anti-aging coupling agent:
a1, weighing p-phenylenediamine, putting into a flask, adding absolute ethyl alcohol, heating to 60 ℃, and stirring at a constant temperature until the p-phenylenediamine is completely dissolved;
a2, adding gamma-urea propyl triethoxysilane, reacting for 10 hours at a constant temperature of 85 ℃ in a nitrogen atmosphere, and then cooling to room temperature to obtain the anti-aging coupling agent;
B. respectively adding graphene oxide and white carbon black into deionized water for ultrasonic dispersion, then mixing a graphene oxide solution and a white carbon black solution, wherein the mass ratio of the graphene oxide to the white carbon black is 1:10, adding ammonia water to adjust the pH to 8, and continuing ultrasonic treatment for 12 hours;
C. adding the ultrasonic graphene oxide and white carbon black mixed solution into a reactor, adding the anti-aging coupling agent prepared in the step A, and stirring at 55 ℃ for reaction for 12 hours;
D. and after the reaction is finished, carrying out vacuum filtration on the reactant, washing the reactant for 3-5 times by using absolute ethyl alcohol and deionized water, and then drying the reactant for 24 hours at 50 ℃ to prepare the anti-aging coupling agent-GO-white carbon black composite material.
Example 5
The preparation method of the composite filler comprises the following steps:
A. grafting p-phenylenediamine into coupling agent gamma-urea propyl triethoxysilane to prepare the anti-aging coupling agent:
a1, weighing p-phenylenediamine, putting into a flask, adding absolute ethyl alcohol, heating to 70 ℃, and stirring at constant temperature until the p-phenylenediamine is completely dissolved;
a2, adding gamma-urea propyl triethoxysilane, reacting for 12 hours at the constant temperature of 80 ℃ in a nitrogen atmosphere, and then cooling to room temperature to obtain the anti-aging coupling agent;
B. respectively adding graphene oxide and white carbon black into deionized water for ultrasonic dispersion, then mixing a graphene oxide solution and a white carbon black solution, wherein the mass ratio of the graphene oxide to the white carbon black is 1:20, adding ammonia water to adjust the pH to 8, and continuing ultrasonic treatment for 8 hours;
C. adding the ultrasonic graphene oxide and white carbon black mixed solution into a reactor, adding the anti-aging coupling agent prepared in the step A, and stirring at 65 ℃ for reaction for 8 hours;
D. and after the reaction is finished, carrying out vacuum filtration on the reactant, washing the reactant for 3-5 times by using absolute ethyl alcohol and deionized water, and then drying the reactant for 12 hours at 60 ℃ to prepare the anti-aging coupling agent-GO-white carbon black composite material.
Example 6
The preparation method of the composite filler comprises the following steps:
A. grafting p-phenylenediamine into coupling agent gamma-urea propyl triethoxysilane to prepare the anti-aging coupling agent:
a1, weighing p-phenylenediamine, putting into a flask, adding absolute ethyl alcohol, heating to 65 ℃, and stirring at constant temperature until the p-phenylenediamine is completely dissolved;
a2, adding gamma-urea propyl triethoxysilane, reacting for 11 hours at the constant temperature of 82 ℃ in a nitrogen atmosphere, and then cooling to room temperature to obtain the anti-aging coupling agent;
B. respectively adding graphene oxide and white carbon black into deionized water for ultrasonic dispersion, then mixing a graphene oxide solution and a white carbon black solution, wherein the mass ratio of the graphene oxide to the white carbon black is 1:15, adding ammonia water to adjust the pH to 8, and continuing ultrasonic treatment for 10 hours;
C. adding the ultrasonic graphene oxide and white carbon black mixed solution into a reactor, adding the anti-aging coupling agent prepared in the step A, and stirring at 60 ℃ for reaction for 10 hours;
D. and after the reaction is finished, carrying out vacuum filtration on the reactant, washing the reactant for 3-5 times by using absolute ethyl alcohol and deionized water, and then drying the reactant for 18 hours at 55 ℃ to prepare the anti-aging coupling agent-GO-white carbon black composite material.
The SEM photograph of the anti-aging coupling agent-GO-white carbon black composite material prepared in example 6 is shown in fig. 2, and as can be seen from fig. 2, after the graphene oxide sheet layer is covered with white carbon black particles, the graphene oxide sheet layer presents a loose structure, and the composite structure is beneficial to the dispersion of the anti-aging coupling agent-GO-white carbon black composite filler in rubber.
Example 7
The preparation method of the modified aramid fiber comprises the following steps:
i, epoxy resin, caprolactam blocked isocyanate and deionized water are mixed according to the mass ratio of 1:5:50, mixing to obtain a pretreatment liquid;
II, resorcinol and formaldehyde are mixed according to the mass ratio of 1:5, adding deionized water, uniformly mixing, reacting for 4 hours at normal temperature, and stirring for 2 hours at butyl pyridine latex with the total mass of resorcinol and formaldehyde being 10 times to obtain RFL dipping liquid;
III, immersing the aramid fiber in the pretreatment liquid for 10s, drying at 160 ℃ for 60s, and curing at 230 ℃ for 60s. The method comprises the steps of carrying out a first treatment on the surface of the
IV, dipping the pretreated aramid fiber into RFL dipping solution for 30s, then drying at 150 ℃ for 90s, and then curing at 220 ℃ for 90s to obtain the modified aramid fiber.
Example 8
The preparation method of the modified aramid fiber comprises the following steps:
i, epoxy resin, caprolactam blocked isocyanate and deionized water are mixed according to the mass ratio of 1:5:50, mixing to obtain a pretreatment liquid;
II, resorcinol and formaldehyde are mixed according to the mass ratio of 1:5, adding deionized water, uniformly mixing, reacting for 4-6 hours at normal temperature, and stirring for 1 hour at butyl pyridine latex with the total mass of resorcinol and formaldehyde being 10 times to obtain RFL dipping liquid;
III, soaking the aramid fiber in the pretreatment liquid for 15s, drying at 150 ℃ for 90s, and curing at 220 ℃ for 90s. The method comprises the steps of carrying out a first treatment on the surface of the
And IV, dipping the pretreated aramid fiber into RFL dipping solution for 20-30 s, drying at 160 ℃ for 60s, and curing at 230 ℃ for 60s to obtain the modified aramid fiber.
Example 9
The preparation method of the modified aramid fiber comprises the following steps:
i, epoxy resin, caprolactam blocked isocyanate and deionized water are mixed according to the mass ratio of 1:5:50, mixing to obtain a pretreatment liquid;
II, resorcinol and formaldehyde are mixed according to the mass ratio of 1:5, adding deionized water, uniformly mixing, reacting for 4-6 hours at normal temperature, and stirring for 2 hours at butyl pyridine latex with the total mass of resorcinol and formaldehyde being 10 times to obtain RFL dipping liquid;
III, soaking the aramid fiber in the pretreatment liquid for 12s, drying at 155 ℃ for 75s, and curing at 225 ℃ for 75s. The method comprises the steps of carrying out a first treatment on the surface of the
IV, dipping the pretreated aramid fiber into RFL dipping solution for 25s, drying at 155 ℃ for 75s, and curing at 225 ℃ for 75s to obtain the modified aramid fiber.
Example 10
The high-strength sole adhesive comprises the following components in parts by weight: 30 parts of modified natural rubber, 70 parts of styrene-butadiene rubber, 20 parts of nitrile rubber, 15 parts of composite filler, 5 parts of modified aramid fiber, 0.5 part of anti-aging agent, 0.1 part of accelerator and 3 parts of sulfur.
The production process of the high-strength sole adhesive comprises the following steps: adding the modified natural rubber, the styrene-butadiene rubber and the nitrile rubber into a rubber open mill for molding, adding the composite filler, the modified aramid fiber and the anti-aging agent for mixing for 3-5 min after the molding is uniform, adding the sulfur and the accelerator for mixing uniformly, and vulcanizing for 8-10 min at 140 ℃ to obtain the high-strength sole rubber sheet.
Example 11
The high-strength sole adhesive comprises the following components in parts by weight: 40 parts of modified natural rubber, 50 parts of styrene-butadiene rubber, 30 parts of nitrile rubber, 10 parts of composite filler, 10 parts of modified aramid fiber, 0.1 part of anti-aging agent, 0.5 part of accelerator and 1 part of sulfur;
the process for producing the high-strength sole adhesive is the same as in example 10.
Example 12
The high-strength sole adhesive comprises the following components in parts by weight: 35 parts of modified natural rubber, 60 parts of styrene-butadiene rubber, 25 parts of nitrile rubber, 12 parts of composite filler, 8 parts of modified aramid fiber, 0.2 part of anti-aging agent, 0.2 part of accelerator and 2 parts of sulfur;
the process for producing the high-strength sole adhesive is the same as in example 10.
Comparative example 1
The high-strength sole adhesive comprises the following components in parts by weight: 35 parts of unmodified natural rubber, 60 parts of styrene-butadiene rubber, 25 parts of nitrile rubber, 12 parts of composite filler, 8 parts of modified aramid fiber, 0.2 part of anti-aging agent, 0.2 part of accelerator and 2 parts of sulfur;
the process for producing the high-strength sole adhesive is the same as in example 10.
Comparative example 2
The high-strength sole adhesive comprises the following components in parts by weight: 35 parts of modified natural rubber, 60 parts of styrene-butadiene rubber, 25 parts of nitrile rubber, 4 parts of graphene oxide, 8 parts of white carbon black, 8 parts of modified aramid fiber, 0.2 part of anti-aging agent, 0.2 part of accelerator and 2 parts of sulfur;
the process for producing the high-strength sole adhesive is the same as in example 10.
Comparative example 3
The high-strength sole adhesive comprises the following components in parts by weight: 35 parts of modified natural rubber, 60 parts of styrene-butadiene rubber, 25 parts of nitrile rubber, 12 parts of composite filler, 0.2 part of anti-aging agent, 0.2 part of accelerator and 2 parts of sulfur;
the process for producing the high-strength sole adhesive is the same as in example 10.
Performance detection
(1) The high-strength sole adhesives prepared in examples 10 to 12 and comparative examples 1 to 3 were subjected to the following mechanical property tests: tensile properties were tested according to GB/T528-2009, with the bars being dumbbell-shaped; the tearing strength is tested according to GB/T529-2008, and the sample bar is a right angle; hardness was tested according to GB/T531.1-2008; the resilience was tested according to GB/T1681-2009, giving the data shown in Table 1 below.
Table 1 results of mechanical property test of high strength sole gum
As can be seen from the data in Table 1, the high-strength sole adhesives prepared in examples 10 to 12 of the present invention have the characteristics of high tensile strength and difficult fracture. The mechanical properties of the modified natural rubber are not reduced in the comparison document 1, the anti-aging coupling agent is not used for treating the graphene oxide and the white carbon black in the comparison document 2, the modified natural rubber is directly added into the rubber material, the mechanical properties of the material are not obviously reduced, the modified aramid fiber is not added in the comparison document 3, and the mechanical properties of the material are obviously reduced.
(2) The high-strength sole adhesives prepared in examples 10 to 12 and comparative examples 1 to 3 were aged at 100℃for 24 hours and 48 hours, respectively, and the changes in tensile strength and tear strength were measured to obtain the data shown in Table 2 below.
Table 2 high strength sole gum aging performance test
As can be seen from the data in Table 2, the high-strength sole glue prepared in the examples 10-12 has higher tensile strength and tearing strength after aging for 24h and 48h, and is proved to have excellent ageing resistance, wherein in the comparative example 2, the tensile strength and tearing strength are obviously reduced after aging because the graphene oxide and white carbon black composite filler are not modified by the anti-aging coupling agent prepared in the invention.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (9)
1. The high-strength sole adhesive is characterized by comprising the following components in parts by weight: 30-40 parts of modified natural rubber, 50-70 parts of styrene-butadiene rubber, 20-30 parts of nitrile rubber, 10-15 parts of composite filler, 5-10 parts of modified aramid fiber, 0.1-0.5 part of anti-aging agent, 0.1-0.5 part of accelerator and 1-3 parts of sulfur;
the modified natural rubber is diacetone acrylamide grafted modified natural rubber;
the composite filler is an anti-aging coupling agent-GO-white carbon black composite material, and the anti-aging coupling agent is p-phenylenediamine grafted gamma-urea propyl triethoxysilane;
the modified aramid fiber is obtained by treating aramid nanofiber with caprolactam-blocked isocyanate and then dipping RFL (rfL) dipping solution, wherein the RFL dipping solution is resorcinol, formaldehyde and butyl pyridine emulsion.
2. The high-strength sole adhesive according to claim 1, wherein the anti-aging agent is one or more of an anti-aging agent D, an anti-aging agent AW, an anti-aging agent DNP, an anti-aging agent 4020, an anti-aging agent 4010NA, and the accelerator is one or more of DM, an accelerator M, an accelerator TMTD, and an accelerator D.
3. The high-strength sole compound of claim 1, wherein the method for preparing the modified natural rubber comprises the following steps:
(1) Adding natural rubber latex into constant temperature water bath equipment, adding sodium dodecyl benzene sulfonate and ammonia water, and stirring at room temperature for 20-40 min under the protection of nitrogen;
(2) Adding benzoyl peroxide chloride into a reaction system, heating to 50-55 ℃, and slowly adding diacetone acrylamide and triethyl phosphonoacetate for 1-3 hours;
(3) And (3) carrying out heat preservation reaction for 3-5 hours, and carrying out vacuum drying at 70 ℃ to balance weight after the latex is coagulated, so as to obtain the modified natural rubber.
4. The high strength sole glue of claim 1, wherein the method of preparing the composite filler comprises the steps of:
A. grafting p-phenylenediamine into coupling agent gamma-urea propyl triethoxysilane to prepare an anti-aging coupling agent;
B. respectively adding graphene oxide and white carbon black into deionized water for ultrasonic dispersion, then mixing a graphene oxide solution and a white carbon black solution, adding ammonia water to adjust the pH value to 8, and continuing ultrasonic treatment for 8-12 hours;
C. adding the ultrasonic graphene oxide and white carbon black mixed solution into a reactor, adding the anti-aging coupling agent prepared in the step A, and stirring at 55-65 ℃ for reaction for 8-12 hours;
D. and after the reaction is finished, carrying out vacuum filtration on the reactant, washing the reactant for 3 to 5 times by using absolute ethyl alcohol and deionized water, and then drying the reactant at 50 to 60 ℃ for 12 to 24 hours to obtain the anti-aging coupling agent-GO-white carbon black composite material.
5. The high strength sole glue according to claim 4, wherein the chemical reaction equation of the anti-aging coupling agent synthesis in the step a is as follows:
；
the preparation method specifically comprises the following steps:
a1, weighing p-phenylenediamine, putting the p-phenylenediamine into a flask, adding absolute ethyl alcohol, heating to 60-70 ℃, and stirring at a constant temperature until the p-phenylenediamine is completely dissolved;
and A2, adding gamma-urea propyl triethoxysilane, reacting for 10-12 hours at the constant temperature of 80-85 ℃ in a nitrogen atmosphere, and then cooling to room temperature to obtain the anti-aging coupling agent.
6. The high-strength sole adhesive according to claim 4, wherein graphene oxide and white carbon black in the step B are mixed according to a mass ratio of 1:10-20.
7. The high strength sole glue of claim 1, wherein the method for preparing the modified aramid fiber comprises the following steps:
i, mixing epoxy resin, caprolactam blocked isocyanate and deionized water in proportion to prepare pretreatment liquid;
adding resorcinol and formaldehyde into deionized water, uniformly mixing, reacting for 4-6 hours at normal temperature, adding butadiene-pyridine latex, and stirring for 1-2 hours to obtain RFL (RFL dipping solution), wherein the mass ratio of resorcinol to formaldehyde to butadiene-pyridine latex is 1:1:10;
III, soaking the aramid fiber in the pretreatment liquid for 10-15 s, drying at 150-160 ℃ for 60-90 s, and curing at 220-230 ℃ for 60-90 s;
and IV, dipping the pretreated aramid fiber into RFL dipping solution for 20-30 s, drying at 150-160 ℃ for 60-90 s, and curing at 220-230 ℃ for 60-90 s to obtain the modified aramid fiber.
8. The high strength sole gum according to claim 7 wherein the mass ratio of epoxy resin, caprolactam blocked isocyanate and deionized water in step i is 1:5:60.
9. the production process of the high-strength sole adhesive is characterized by comprising the following steps of: adding the modified natural rubber, the styrene-butadiene rubber and the nitrile rubber into a rubber open mill for molding, adding the composite filler, the modified aramid fiber and the anti-aging agent for mixing for 3-5 min after the molding is uniform, adding the sulfur and the accelerator for mixing uniformly, and vulcanizing for 8-10 min at 140 ℃ to obtain the high-strength sole rubber sheet.
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