CN114921007A - Preparation method of wear-resistant rain shoes - Google Patents
Preparation method of wear-resistant rain shoes Download PDFInfo
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- CN114921007A CN114921007A CN202210758941.6A CN202210758941A CN114921007A CN 114921007 A CN114921007 A CN 114921007A CN 202210758941 A CN202210758941 A CN 202210758941A CN 114921007 A CN114921007 A CN 114921007A
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- wear
- agent
- resistant
- micro powder
- rain
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 66
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 54
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 239000005060 rubber Substances 0.000 claims abstract description 35
- 239000000945 filler Substances 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 23
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000004902 Softening Agent Substances 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 230000005251 gamma ray Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 230000006750 UV protection Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 8
- 239000013543 active substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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
- A43B1/00—Footwear characterised by the material
- A43B1/10—Footwear characterised by the material made of rubber
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B7/00—Footwear with health or hygienic arrangements
- A43B7/12—Special watertight footwear
-
- 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of wear-resistant rain shoes, which belongs to the technical field of rain shoe preparation and comprises the following steps: step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder into a screw extruder, and extruding and granulating to obtain the wear-resistant filler; step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 60-80 ℃, and plastifying for 5-6 min; then sequentially adding a softening agent, an activating agent, an anti-aging agent, a wear-resistant filler, an accelerator and a cross-linking agent, heating to 90-120 ℃, and banburying for 20-30min to obtain a rubber compound; and heating the rubber compound in an open mill to 50-90 ℃, and then putting the rubber compound in a rain boot mold for vulcanization molding to obtain the wear-resistant rain boot. The wear-resistant filler is white carbon black particles coated with grafted polytetrafluoroethylene, has an inorganic-organic core-shell structure, and greatly improves the wear resistance and the ultraviolet resistance of the rain boot.
Description
Technical Field
The invention belongs to the technical field of rain shoe preparation, and particularly relates to a preparation method of a wear-resistant rain shoe.
Background
Rain shoes are common polymer material products in daily life. Most of the rain shoes sold in the market at present are made of natural rubber or synthetic rubber, and the wear resistance of the rain shoes is poor. In order to improve the wear resistance of rain shoes, various wear-resistant aids are generally added to the rain shoes. For example, in the method for preparing the graphene oxide/white carbon black/rubber nanocomposite disclosed in chinese patent application CN102604175A, the modified styrene-butadiene rubber co-filled with graphene oxide and modified white carbon black is prepared by a solution blending method or a mechanical blending method. The wear resistance of the styrene butadiene rubber is improved by the graphene oxide and the modified white carbon black. However, in the above patent, graphene oxide is uniformly dispersed in styrene butadiene rubber only through physical action, and in a long-term use process, graphene oxide inevitably migrates and aggregates, which causes a decrease in various performances of the rain boot and shortens a service life of the rain boot.
Therefore, the technical problem to be solved in the technical field of the existing rain shoes is to provide the wear-resistant and durable rain shoes.
Disclosure of Invention
The invention aims to provide a preparation method of wear-resistant rain shoes, which aims to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of wear-resistant rain shoes comprises the following steps:
step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder into a screw extruder, and extruding and granulating to obtain the wear-resistant filler, wherein the mass ratio of the pretreated white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 1-3;
step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 60-80 ℃, and plastifying for 5-6 min; then sequentially adding a softening agent, an activating agent, an anti-aging agent, a wear-resistant filler, an accelerator and a cross-linking agent, heating to 90-120 ℃, and banburying for 20-30min to obtain a rubber compound; heating the rubber compound to 50-90 ℃ in an open mill, and then placing the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 160-175 ℃, the molding pressure is 11-13MPa, and the molding time is 20-40min, so as to obtain the wear-resistant rain shoe.
Further, the grafting-treated polytetrafluoroethylene micro powder is prepared by the following steps:
carrying out irradiation treatment on the polytetrafluoroethylene micro powder to obtain the irradiation treated polytetrafluoroethylene micro powder, wherein the irradiation conditions are as follows: in the state of air, the air is in a room, 60 co source gamma ray with the irradiation dose of 40-70 kGy; and then uniformly mixing the polytetrafluoroethylene micro powder subjected to irradiation treatment, acrylic acid, vinyl siloxane, an anti-ultraviolet agent and toluene, adding a polymerization inhibitor and sulfuric acid, heating to 60-65 ℃, stirring for reaction for 2-3 hours, performing suction filtration, washing with water and alcohol for several times, and drying to obtain the polytetrafluoroethylene micro powder subjected to grafting treatment, wherein the mass ratio of the polytetrafluoroethylene micro powder, the acrylic acid, the vinyl siloxane, the anti-ultraviolet agent and the polymerization inhibitor is 10-15:0.5-2:1.5-3:1-2:0.3-0.5, and the polymerization inhibitor is methyl hydroquinone.
In the reaction, firstly, the polytetrafluoroethylene micro powder is irradiated to generate a plurality of free radicals and peroxides, then the polytetrafluoroethylene micro powder with the characteristics is mixed with double bond monomers such as acrylic acid, vinyl siloxane, an anti-ultraviolet agent and the like, and the free radicals and the peroxides react with the double bonds to connect polar groups (carboxyl groups), siloxane chains and structures for absorbing ultraviolet rays on the surface of the polytetrafluoroethylene micro powder, wherein the polar groups enable the polytetrafluoroethylene micro powder to be uniformly dispersed in a rubber matrix, and meanwhile, the polytetrafluoroethylene micro powder and white carbon black have good adsorbability, so that the polytetrafluoroethylene micro powder is wrapped on the surface of the white carbon black to form an inorganic-organic core-shell structure, and the contained siloxane chains not only improve the wettability of the polytetrafluoroethylene micro powder, but also further promote the dispersibility of the polytetrafluoroethylene micro powder in the rubber matrix, and the function of a coupling agent can be exerted, so that the white carbon black and the polyethylene micro powder are bridged through a silicon-oxygen chain, the stability and the durability of the inorganic-organic core-shell structure are promoted, and the ultraviolet absorption structure endows the grafted polytetrafluoroethylene micro powder with ultraviolet resistance.
Further, the uvioresistant agent is double-bonded 2, 4-dihydroxy benzophenone and/or 2- (2' -hydroxy-5-methylphenyl) benzotriazole.
Further, the double-bonded 2, 4-dihydroxybenzophenone is obtained by taking 2, 4-dihydroxybenzophenone and acryloyl chloride as reaction substrates, triethylamine or potassium carbonate as an acid-binding agent, one of dichloromethane and tetrahydrofuran as a solvent, and stirring and reacting at 0-30 ℃ for 2-10h, wherein the molar ratio of the 2, 4-dihydroxybenzophenone to the acryloyl chloride to the acid-binding agent is 1:1:1.2-1.4, and the adding mass of the solvent is 4-8 times of the mass of the reaction substrates.
Further, the double-bonded 2- (2 '-hydroxy-5-methylphenyl) benzotriazole is obtained by stirring and reacting 2- (2' -hydroxy-5-methylphenyl) benzotriazole and acryloyl chloride serving as reaction substrates at 0-30 ℃ for 2-10h by using triethylamine or potassium carbonate as an acid-binding agent and one of dichloromethane and tetrahydrofuran as a solvent, wherein the mass of the added solvent is 4-8 times of that of the reaction substrates.
Further, in the third step, the mass ratio of the styrene-butadiene rubber, the acrylate rubber, the softening agent, the activating agent, the anti-aging agent, the wear-resistant filler, the accelerator and the crosslinking agent is 90-130:10-30:6-14:3-7:1-3.5:40-70:2-6: 1.5-5.5.
Further, the softening agent is one or a mixture of several of aromatic oil, paraffin and vaseline in any ratio.
Further, the active agent is one or a mixture of two of stearic acid and zinc oxide in any ratio.
Furthermore, the anti-aging agent is one or a mixture of more of anti-aging agent 4010 and anti-aging agent RD.
Further, the accelerator is one or a mixture of more of accelerator DM, accelerator TT and accelerator TBBS in any ratio.
Further, the cross-linking agent is N, N' -m-phenylene bismaleimide, dicumyl peroxide, sulfur, benzoyl peroxide or 2, 4-dichlorobenzoyl peroxide.
The invention has the beneficial effects that:
in order to solve the problems in the background art, the invention introduces acrylate rubber and wear-resistant filler into styrene-butadiene rubber base material, the wear-resistant filler is grafted polytetrafluoroethylene to wrap white carbon black particles, and has an inorganic-organic core-shell structure (a hard core and a soft chain shell structure), so that the lubricating characteristic of the rigid spherical particles of the white carbon black can be exerted, the characteristics of low acting force among friction molecules and easy slippage among the molecular layers of the polytetrafluoroethylene can be exerted, the wear resistance of the rain boot is greatly improved, the inorganic-organic core-shell structure can be exerted, the elastic property of the rain boot is improved, the grafted polytetrafluoroethylene is grafted with an ultraviolet absorption structure, and the introduction of the grafted polytetrafluoroethylene improves the ultraviolet resistance of the rain boot; and the surface of the wear-resistant filler contains free double bonds (introduced by grafted polytetrafluoroethylene) and can be crosslinked with acrylic ester in the raw materials, so that the processing performance between the wear-resistant filler and styrene butadiene rubber is further improved, and the integrity of the composite material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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
Preparing grafted polytetrafluoroethylene micropowder:
carrying out irradiation treatment on 10g of polytetrafluoroethylene micro powder to obtain the irradiation-treated polytetrafluoroethyleneMicropowder, wherein the irradiation conditions are as follows: the state of the air is that the air is, 60 co source gamma ray with the irradiation dose of 40 kGy; then, after 10g of irradiation-treated polytetrafluoroethylene micro powder, 0.5g of acrylic acid, 1.5g of vinyl siloxane, 1g of anti-ultraviolet agent and 120mL of toluene are uniformly mixed, 0.3g of polymerization inhibitor and 0.5g of 0.1M sulfuric acid are added, the mixture is heated to 60 ℃, stirred and reacted for 3 hours, and subjected to suction filtration, water washing and alcohol washing for 3 times, and drying to obtain graft-treated polytetrafluoroethylene micro powder, wherein the polymerization inhibitor is methyl hydroquinone;
the uvioresistant agent is double-bonded 2, 4-dihydroxy benzophenone and is prepared by the following steps:
uniformly mixing 2, 4-dihydroxy benzophenone 0.1mol, triethylamine 0.13mol and dichloromethane, slowly dropwise adding dichloromethane containing acryloyl chloride at 0 ℃, heating to room temperature after completely dropwise adding, continuously stirring for reaction for 4h, carrying out reduced pressure rotary evaporation, then recrystallizing with methanol, and drying to obtain the double-bonded 2, 4-dihydroxy benzophenone.
Example 2
Preparing grafted polytetrafluoroethylene micropowder:
carrying out irradiation treatment on 15g of polytetrafluoroethylene micro powder to obtain the irradiation-treated polytetrafluoroethylene micro powder, wherein the irradiation conditions are as follows: the state of the air is that the air is, 60 co source gamma ray with the irradiation dose of 70 kGy; then, after 15g of irradiation-treated polytetrafluoroethylene micro powder, 2g of acrylic acid, 3g of vinyl siloxane, 2g of ultraviolet resistant agent and 120mL of toluene are uniformly mixed, 0.5g of polymerization inhibitor and 0.8g of 0.1M sulfuric acid are added, the mixture is heated to 65 ℃, stirred and reacted for 2 hours, and subjected to suction filtration, washing with water and alcohol for several times, and drying to obtain the graft-treated polytetrafluoroethylene micro powder, wherein the polymerization inhibitor is methyl hydroquinone;
the uvioresistant agent is double-bonded 2- (2' -hydroxy-5-methylphenyl) benzotriazole and is prepared by the following steps:
uniformly mixing 2- (2 '-hydroxy-5-methylphenyl) benzotriazole 0.1mol, triethylamine 0.14mol and tetrahydrofuran, slowly dropwise adding tetrahydrofuran containing acryloyl chloride at 0 ℃, heating to room temperature after completely dropwise adding, continuously stirring for reacting for 6h, decompressing and rotary evaporating, then recrystallizing with methanol, and drying to obtain the double-bonded 2- (2' -hydroxy-5-methylphenyl) benzotriazole.
Example 3
Preparation of a wear-resistant rain shoe:
step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder prepared in the example 1 into a screw extruder, and extruding and granulating to obtain the wear-resistant filler, wherein the mass ratio of the pretreated white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 1;
step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 70 ℃, and plastifying for 5 min; then sequentially adding a softening agent, an active agent, an anti-aging agent, a wear-resistant filler, an accelerator and a cross-linking agent, heating to 100 ℃, and banburying for 25min to obtain a rubber compound; heating the rubber compound to 60 ℃ in an open mill, putting the rubber compound into a rain shoe mold, and vulcanizing and molding at the molding temperature of 160 ℃, the molding pressure of 11MPa and the molding time of 40min to obtain the wear-resistant rain shoe, wherein in the third step, the mass ratio of the styrene-butadiene rubber, the acrylate rubber, the softener, the activator, the anti-aging agent, the wear-resistant filler, the accelerator and the crosslinking agent is 90:30:6:3:1:40:2: 1.5; the softening agent is aromatic oil; the active agent is stearic acid; the anti-aging agent is anti-aging agent 4010 and anti-aging agent RD; the accelerator is an accelerator DM; the cross-linking agent is N, N' -m-phenylene bismaleimide.
Example 4
Preparation of a wear-resistant rain shoe:
step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder prepared in the embodiment 2 into a screw extruder, and extruding and granulating to obtain the wear-resistant filler, wherein the mass ratio of the pretreated white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 2;
step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 60 ℃, and plastifying for 6 min; then sequentially adding a softening agent, an active agent, an anti-aging agent, a wear-resistant filler, an accelerator and a crosslinking agent, heating to 90 ℃, and banburying for 30min to obtain a rubber compound; heating the rubber compound to 50 ℃ in an open mill, putting the rubber compound into a rain shoe mold, and vulcanizing and molding at the molding temperature of 160 ℃, the molding pressure of 11MPa and the molding time of 40min to obtain the wear-resistant rain shoe, wherein in the third step, the mass ratio of the styrene-butadiene rubber, the acrylate rubber, the softener, the activator, the anti-aging agent, the wear-resistant filler, the accelerator and the crosslinking agent is 110:20:10:5:2:60:4: 3; the softening agent is paraffin; the activator is formed by mixing stearic acid and zinc oxide according to the mass ratio of 2: 1; the anti-aging agent is an anti-aging agent 4010; the accelerant is a promoting agent TT; the cross-linking agent is dicumyl peroxide.
Example 5
Preparation of a wear-resistant rain shoe:
step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder prepared in the example 1 into a screw extruder, and extruding and granulating to obtain the wear-resistant filler, wherein the mass ratio of the pretreated white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 3;
step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 80 ℃, and plastifying for 5 min; then sequentially adding a softener, an active agent, an anti-aging agent, a wear-resistant filler, an accelerator and a cross-linking agent, heating to 120 ℃, and banburying for 20min to obtain a rubber compound; heating the rubber compound in an open mill to 90 ℃, putting the rubber compound in a rain boot mold, and vulcanizing and molding the rubber compound at the molding temperature of 175 ℃, the molding pressure of 13MPa and the molding time of 20min to obtain the wear-resistant rain boot, wherein the mass ratio of the styrene butadiene rubber, the acrylate rubber, the softening agent, the active agent, the anti-aging agent, the wear-resistant filler, the accelerator and the crosslinking agent is 130:10:14:7:3.5:70:6: 5.5; the softener is vaseline; the active agent is zinc oxide; the anti-aging agent is an anti-aging agent 4010; the accelerator is an accelerator DM; the cross-linking agent is 2, 4-dichlorobenzoyl peroxide.
Comparative example 1
Preparation of a wear-resistant rain shoe: compared with the embodiment 3, the wear-resistant filler is equivalently replaced by the wear-resistant filler prepared by the following steps, and the rest is the same:
carrying out irradiation treatment on 10g of polytetrafluoroethylene micro powder to obtain the irradiation-treated polytetrafluoroethylene micro powder, wherein the irradiation conditions are as follows: in the state of air, the air is in a room, 60 co source gamma rays, wherein the irradiation dose is 40 kGy; then, after 10g of irradiation-treated polytetrafluoroethylene micro powder, 0.5g of acrylic acid, 1.5g of vinyl siloxane and 120mL of toluene are uniformly mixed, 0.3g of polymerization inhibitor and 0.5g of sulfuric acid are added, the mixture is heated to 60 ℃, stirred and reacted for 3 hours, filtered, washed with water and alcohol for 3 times, and dried to obtain graft-treated polytetrafluoroethylene micro powder, wherein the polymerization inhibitor is methyl hydroquinone;
adding the white carbon black and the prepared grafted polytetrafluoroethylene micro powder into a screw extruder, extruding and granulating to obtain the wear-resistant filler, wherein the mass ratio of the pretreated white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 1.
Comparative example 2
Preparation of a wear-resistant rain shoe: compared with the embodiment 4, the abrasion-resistant filler is replaced by white carbon black with the same quantity, and the rest is the same.
Comparative example 3
Preparation of a wear-resistant rain shoe: in comparison with example 5, the abrasion resistant filler was replaced with the graft-treated polytetrafluoroethylene fine powder prepared in example 1 in the same amount, and the rest was the same.
Example 6
The rain shoes obtained in examples 3 to 5 and comparative examples 1 to 3 were subjected to the following performance tests:
wear loss: cutting rain shoes into samples of 6cm multiplied by 2.5cm multiplied by 1.5, weighing and weighing m0, then using the samples in a wear test, brushing floating chips with a brush after the test is finished, weighing and weighing m1, wherein the rotation speed of a grinding wheel (a grinding disc) is 1000r/min, the test time is 5min, the surface granularity of the grinding wheel is 60#, the load is 800g, each sample is tested for 3 times, the average value is taken, the wear loss is calculated according to the following formula, and the wear loss is (m0-m 1)/5;
ultraviolet aging resistance: after irradiating for 50 days according to GB/T16422.3, testing the elastic property of the rubber;
the elastic property: testing according to ASTM D638;
the data obtained from the above tests are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the abrasion resistance of the rain boots obtained in examples 3 to 5 is superior to that of the rain boots obtained in comparative examples 2 to 3, the ultraviolet aging resistance of the rain boots obtained in examples 3 to 5 is superior to that of the rain boots obtained in comparative example 1, and the rain boots obtained in examples 3 to 5 have good elastic properties.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of wear-resistant rain shoes is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing wear-resistant filler: adding the white carbon black and the grafted polytetrafluoroethylene micro powder into a screw extruder, and extruding and granulating to obtain the wear-resistant filler;
step two, mixing and forming: adding styrene butadiene rubber and acrylate rubber into an open mill, controlling the roll temperature at 60-80 ℃, and plastifying for 5-6 min; then sequentially adding a softener, an activator, an anti-aging agent, a wear-resistant filler, an accelerator and a cross-linking agent, heating to 90-120 ℃, and banburying for 20-30min to obtain a rubber compound; and heating the rubber compound in an open mill to 50-90 ℃, and then putting the rubber compound in a rain boot mold for vulcanization molding to obtain the wear-resistant rain boot.
2. The method of manufacturing a wear-resistant rain shoe according to claim 1, wherein: in the first step, the mass ratio of the white carbon black to the grafted polytetrafluoroethylene micro powder is 10: 1-3.
3. The method of claim 1, wherein the method comprises the steps of: in the second step, the mass ratio of the styrene butadiene rubber, the acrylate rubber, the softening agent, the activating agent, the anti-aging agent, the wear-resistant filler, the accelerator and the crosslinking agent is 90-130:10-30:6-14:3-7:1-3.5:40-70:2-6: 1.5-5.5.
4. The method of claim 1, wherein the method comprises the steps of: in the second step, the molding temperature is 160-.
5. The method of manufacturing a wear-resistant rain shoe according to claim 1, wherein: the grafted polytetrafluoroethylene micropowder is prepared by the following steps:
carrying out irradiation treatment on the polytetrafluoroethylene micro powder to obtain the irradiated polytetrafluoroethylene micro powder; then uniformly mixing the irradiated polytetrafluoroethylene micro powder, acrylic acid, vinyl siloxane, an anti-ultraviolet agent and toluene, adding a polymerization inhibitor and sulfuric acid, stirring and reacting for 2-3h at the temperature of 60-65 ℃, and performing suction filtration, water washing, alcohol washing and drying to obtain the grafted polytetrafluoroethylene micro powder.
6. The method of claim 5, wherein the method comprises the steps of: the mass ratio of the polytetrafluoroethylene micro powder to the acrylic acid to the vinyl siloxane to the anti-ultraviolet agent to the polymerization inhibitor is 10-15:0.5-2:1.5-3:1-2: 0.3-0.5.
7. The method of claim 5, wherein the method comprises the steps of: irradiation conditions: the state of the air is that the air is, 60 co source gamma ray, the irradiation dose is 40-70 kGy.
8. The method of claim 5, wherein the method comprises the steps of: the uvioresistant agent is double-bonded 2, 4-dihydroxy benzophenone and/or 2- (2' -hydroxy-5-methylphenyl) benzotriazole.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063767A (en) * | 2023-03-11 | 2023-05-05 | 广东安拓普聚合物科技有限公司 | Mining scratch-resistant sheath material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923264A (en) * | 2014-03-19 | 2014-07-16 | 浙江歌瑞新材料有限公司 | Hydrophilic and oleophilic polytetrafluoroethylene micro-powder and preparation method thereof |
| CN104497376A (en) * | 2014-11-26 | 2015-04-08 | 青岛崂乡茶制品有限公司 | Flame-retardation rubber sole |
| CN105820383A (en) * | 2016-05-24 | 2016-08-03 | 宁波市中迪鞋业有限公司 | Composite wear-resisting shoe sole |
| CN106519525A (en) * | 2016-11-24 | 2017-03-22 | 安徽美腾特种电缆材料有限公司 | Engine oil seal rubber material and preparation method thereof |
| CN108239312A (en) * | 2018-01-10 | 2018-07-03 | 无锡宝通科技股份有限公司 | Ptfe micropowder acid and alkali-resistance conveyer belt coating rubber and preparation method thereof |
| CN111303717A (en) * | 2020-02-18 | 2020-06-19 | 吉林大学 | Preparation method of photo-initiated cross-linked anti-fog coating |
-
2022
- 2022-06-29 CN CN202210758941.6A patent/CN114921007A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923264A (en) * | 2014-03-19 | 2014-07-16 | 浙江歌瑞新材料有限公司 | Hydrophilic and oleophilic polytetrafluoroethylene micro-powder and preparation method thereof |
| CN104497376A (en) * | 2014-11-26 | 2015-04-08 | 青岛崂乡茶制品有限公司 | Flame-retardation rubber sole |
| CN105820383A (en) * | 2016-05-24 | 2016-08-03 | 宁波市中迪鞋业有限公司 | Composite wear-resisting shoe sole |
| CN106519525A (en) * | 2016-11-24 | 2017-03-22 | 安徽美腾特种电缆材料有限公司 | Engine oil seal rubber material and preparation method thereof |
| CN108239312A (en) * | 2018-01-10 | 2018-07-03 | 无锡宝通科技股份有限公司 | Ptfe micropowder acid and alkali-resistance conveyer belt coating rubber and preparation method thereof |
| CN111303717A (en) * | 2020-02-18 | 2020-06-19 | 吉林大学 | Preparation method of photo-initiated cross-linked anti-fog coating |
Non-Patent Citations (1)
| Title |
|---|
| 雍铭熙: "新编橡胶制品实用配方及相关技术标准实用手册 中" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063767A (en) * | 2023-03-11 | 2023-05-05 | 广东安拓普聚合物科技有限公司 | Mining scratch-resistant sheath material |
| CN116063767B (en) * | 2023-03-11 | 2023-10-10 | 广东安拓普聚合物科技有限公司 | Mining scratch-resistant sheath material |
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