CN110628102B - Preparation method of ultraviolet light aging-resistant wear-resistant rain shoes - Google Patents
Preparation method of ultraviolet light aging-resistant wear-resistant rain shoes Download PDFInfo
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- CN110628102B CN110628102B CN201910992568.9A CN201910992568A CN110628102B CN 110628102 B CN110628102 B CN 110628102B CN 201910992568 A CN201910992568 A CN 201910992568A CN 110628102 B CN110628102 B CN 110628102B
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- 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
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- 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
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- 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
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a preparation method of an ultraviolet light aging resistant and wear resistant rain shoe, and belongs to the technical field of preparation of high-performance functional rubber shoe materials. The ultraviolet light aging resistant and wear resistant rain boot is prepared by the steps of firstly reacting 2, 4-dihydroxy benzophenone and modified white carbon black with carboxylated graphene oxide in sequence to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, then adding a softening agent, an activating agent, an anti-aging agent, 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, an accelerating agent and a crosslinking agent into styrene butadiene rubber in sequence, and carrying out mixing and vulcanization molding. The rain shoes prepared by the invention have excellent ultraviolet aging resistance, outstanding wear resistance and better mechanical property, have the characteristics of light weight, no toxicity, no pollution, safety, environmental protection and the like, are particularly suitable for areas with higher ultraviolet intensity, such as low-latitude coastal areas, high altitudes and the like, and have higher economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance functional rubber shoe materials, and particularly relates to a preparation method of an ultraviolet light aging-resistant 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 addition, the ultraviolet intensity in low-latitude coastal and high-altitude areas is higher, and the rain shoes used in the areas are easily subjected to photo-aging degradation under the irradiation of high-intensity ultraviolet rays, so that the service life of the rain shoes is seriously reduced. In order to improve the wear resistance and the anti-aging performance of the rain shoes, various wear-resistant additives and anti-aging additives are generally added into the rain shoes. The influence of the common white carbon black and the silane coupling agent Si-69 modified white carbon black on the performance of the solution polymerized styrene-butadiene rubber is researched by the Liu Quanzhang (Liu Quanzhang, Zhaohong, Waihua, Gongguang Bian, plum red, the surface modified white carbon black for enhancing the performance of the solution polymerized styrene-butadiene rubber, the synthetic rubber industry, 2014, 37 (2): 144-. Research results show that compared with the method of directly adding the modified white carbon black, the mechanical property of the solution polymerized styrene-butadiene rubber filled with the modified white carbon black by the pretreatment method is better, and the rubber material has better vulcanization characteristic and wear resistance and lower rolling resistance. The application of panqin (panqin, soldier of king, morning glory; white carbon black with an anti-aging agent grafted on the surface in natural rubber, published in composite materials, 2013, 30 (5): 1-8) adopts a silane coupling agent KH560 and a reactant of p-phenylenediamine to carry out surface modification on the white carbon black, and the white carbon black is used for carrying out filling modification on the natural rubber. Researches show that the modified white carbon black has improved dispersibility in rubber, and the natural rubber filled with the white carbon black has excellent mechanical property and excellent ozone resistance and damp-heat aging resistance. The invention patent CN102604175A of China is used for preparing the modified styrene-butadiene rubber with the co-filled graphene oxide and the modified white carbon black. The result shows that the graphene oxide and the white carbon black can be uniformly dispersed in the rubber matrix, the white carbon black particles fill the gaps between graphene oxide sheets, and the addition of the graphene oxide obviously improves the wear resistance of the styrene butadiene rubber. However, in the patent, the modified white carbon black and the graphene oxide are combined through physical action, and the white carbon black and the graphene oxide inevitably move and gather in position in the long-term use process, so that the mechanical property is reduced.
Disclosure of Invention
Aiming at the defects of poor wear resistance and ultraviolet aging resistance of the conventional rain shoes, the invention provides a preparation method of the ultraviolet aging resistant wear-resistant rain shoes. According to the invention, 2, 4-dihydroxy benzophenone and gamma-aminopropyltriethoxysilane modified white carbon black are sequentially reacted with carboxylated graphene oxide by using a conventional chemical method to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, and the material is used as an ultraviolet light aging resistant auxiliary agent and a wear resistant auxiliary agent and is filled into a styrene butadiene rubber rain boot material to prepare the rain boot which has excellent ultraviolet light aging resistance, outstanding wear resistance and better mechanical property, and is light in weight, nontoxic, pollution-free, safe and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultraviolet light aging resistant and wear resistant rain boot is prepared by sequentially reacting 2, 4-dihydroxy benzophenone and modified white carbon black with carboxylated graphene oxide to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, sequentially adding a softening agent, an activating agent, an anti-aging agent, 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, an accelerator and a cross-linking agent into styrene butadiene rubber, and carrying out mixing and vulcanization molding;
the preparation method of the ultraviolet light aging resistant and wear resistant rain shoes comprises the following steps:
(1) adding 0.002-0.1 g of carboxylated graphene oxide (Wangzhengwei, Xianli, Gaozao, Wang Shafeng, Yan Li, Zhang hong, Jie Zhao, Mao Chang Ying; preparation of carboxylated graphene oxide and electrochemical properties thereof, scientific report of Yunnan national university (Nature science edition), 2013, 22 (2): 86-90) into 10-500 mL of thionyl chloride, heating to 80-100 ℃, and carrying out magnetic stirring reaction for 3-6 h; after the reaction is finished, decompressing and distilling to remove excessive thionyl chloride, fully washing residues with anhydrous tetrahydrofuran, and drying in vacuum at 60 ℃ for 24 hours to prepare the acyl chloride graphene oxide; adding the prepared acyl chloride oxidized graphene into 10-500 mL of N, N-dimethylformamide, carrying out ultrasonic treatment for 20-60 min at room temperature, adding 0.01-0.5 g of 2, 4-dihydroxy benzophenone, heating to 60-80 ℃, carrying out magnetic stirring reaction for 2-6 h, then adding 1-5 g of gamma-aminopropyltriethoxysilane modified white carbon black (chenchenchenhao, wujun, span and Yangrui; technological conditions of coupling agent modified white carbon black are optimized, food industry science and technology, 2014, 35 (14): 131-; after the reaction is finished, performing centrifugal separation, fully washing the separated solid matter with 100-500 mL of absolute ethyl alcohol, and performing vacuum drying at 60 ℃ for 24 hours to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide;
(2) placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 40-50 ℃, and plasticating for 2-4 min; and sequentially adding 6-10 g of softener, 3-5 g of activator, 3-6 g of anti-aging agent, 25-50 g of 2, 4-dihydroxy benzophenone and white carbon black chemically-bonded graphene oxide, 2-5 g of accelerator and 1-5 g of cross-linking agent into the styrene butadiene rubber within 20-30 min. After the addition, continuously passing for 4-8 times, and discharging to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide/styrene-butadiene rubber mixed rubber; and heating the rubber compound in an open mill to 50-90 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 150-170 ℃, the molding pressure is 10-14 MPa, and the molding time is 20-40 min, so as to obtain the ultraviolet light aging resistant and wear resistant rain shoe.
The softening agent is aromatic oil, paraffin or vaseline.
The active agent is zinc oxide or stearic acid.
The anti-aging agent is N-phenyl-alpha-naphthylamine, N-phenyl-N' -cyclohexyl p-phenylenediamine or a calcium-zinc composite stabilizer.
The accelerant is an accelerant 808, an accelerant CZ, an accelerant TBBS, an accelerant NOBS or an accelerant DZ.
The cross-linking agent is N, N' -m-phenylene bismaleimide, dicumyl peroxide, sulfur, benzoyl peroxide or 2, 4-dichloro benzoyl peroxide.
Compared with the prior art, the invention has the following advantages:
(1) the ultraviolet absorbent and the white carbon black are chemically bonded on the surface of the graphene by a chemical method, so that the isolation effect of the ultraviolet absorbent and the white carbon black can be exerted, the graphene is effectively prevented from agglomerating in the styrene butadiene rubber, and the huge specific surface area of the graphene can be utilized to improve the dispersibility of the ultraviolet absorbent and the white carbon black in the styrene butadiene rubber. Meanwhile, the saturated alkyl chain on the chemically bonded graphene oxide of the 2, 4-dihydroxy benzophenone and the white carbon black can also improve the compatibility between the chemically bonded graphene oxide of the 2, 4-dihydroxy benzophenone and the white carbon black and the styrene butadiene rubber, so that the chemically bonded graphene oxide of the 2, 4-dihydroxy benzophenone and the white carbon black is uniformly and stably dispersed in the styrene butadiene rubber.
(2) The 2, 4-dihydroxy benzophenone and the white carbon black chemically bonded graphene oxide which are uniformly and stably dispersed can endow the styrene butadiene rubber with excellent ultraviolet aging resistance, outstanding wear resistance and better mechanical property, and compared with the prior art, the uniformly and stably dispersed state can also reduce the using amount of the white carbon black, so the high-wear-resistance rain boot prepared by the invention has the characteristic of light weight.
(3) The rain shoes prepared by the invention have excellent ultraviolet aging resistance, outstanding wear resistance and better mechanical property, and the abrasion loss is 0.044-0.097 cm3The tensile strength is 30.4-35.9 MPa, the elongation at break is 457-499%, after the ultraviolet light irradiates for 360 days, the abrasion loss is increased by 25.0-54.6%, the tensile strength is reduced by 13.9-28.0%, the elongation at break is reduced by 16.4-39.6%, and the ultraviolet light-resistant composite material is particularly suitable for areas with high ultraviolet intensity such as low-latitude coastal areas, high altitudes and the like, and has high economic value and social benefit.
Drawings
FIG. 1 is an IR spectrum of chemically bonded graphene oxide of 2, 4-dihydroxybenzophenone and silica prepared in example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Adding 0.002 g of carboxylated graphene oxide into 10 mL of thionyl chloride, heating to 80 ℃, and carrying out magnetic stirring reaction for 6 hours; after the reaction is finished, decompressing and distilling to remove excessive thionyl chloride, fully washing residues with anhydrous tetrahydrofuran, and drying in vacuum at 60 ℃ for 24 hours to prepare the acyl chloride graphene oxide; adding the prepared acyl chlorination graphene oxide into 10 mL of N, N-dimethylformamide, performing ultrasonic treatment at room temperature for 20 min, adding 0.01 g of 2, 4-dihydroxy benzophenone, heating to 60 ℃, performing magnetic stirring reaction for 6 h, then adding 1g of gamma-aminopropyltriethoxysilane modified white carbon black, and continuing to perform magnetic stirring reaction for 4 h; after the reaction is finished, performing centrifugal separation, fully washing the separated solid substance by using 100 mL of absolute ethyl alcohol, and performing vacuum drying at 60 ℃ for 24 h to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide;
(2) placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 40 ℃, and plastifying for 4 min; sequentially adding 6g of aromatic oil, 3g of stearic acid, 3g of N-phenyl-alpha-naphthylamine, 25g of 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, 2g of promoter CZ and 1g of N, N' -m-phenylene bismaleimide into the styrene butadiene rubber within 20 min; after the addition, continuously passing for 4 times, and then slicing to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide/styrene butadiene rubber compound; and heating the rubber compound in an open mill to 50 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 150 ℃, the molding pressure is 14 MPa, and the molding time is 40 min, so as to obtain the ultraviolet light aging resistant and wear resistant rain shoe.
FIG. 1 is an IR spectrum of chemically bonded graphene oxide of 2, 4-dihydroxybenzophenone and silica prepared in example 1. As can be seen from the figure, at 3440 cm-1The broader absorption peak is the absorption peak caused by the superposition of the vibration absorption peaks of O-H and N-H in the product, and is 2976 cm-1And 2923 cm-1The obvious absorption peaks are C-H symmetrical and anti-symmetrical vibration absorption peaks in the product, which indicates that saturated alkyl chains exist in the product, and the absorption peak is 1761 cm-1The absorption peak is C = O vibration absorption peak in the product, and is 1596 cm-1And 1503 cm-1The absorption peak is vibration absorption peak of benzene ring C = C in the product, and is 1278 cm-1And 1220 cm-1The absorption peaks are respectively C-Si and C-N vibration absorption peaks in the product and are 1118 cm-1And 1034 cm-1Respectively has an absorption peak ofC-O and Si-O vibration absorption peaks in the product show that the 2, 4-dihydroxy benzophenone and the white carbon black chemically bonded graphene oxide are successfully prepared and a large amount of saturated alkyl chains exist in the product.
Example 2
(1) Adding 0.02 g of carboxylated graphene oxide into 100 mL of thionyl chloride, heating to 90 ℃, and carrying out magnetic stirring reaction for 4.5 h; after the reaction is finished, decompressing and distilling to remove excessive thionyl chloride, fully washing residues with anhydrous tetrahydrofuran, and drying in vacuum at 60 ℃ for 24 hours to prepare the acyl chloride graphene oxide; adding the prepared acyl chlorination graphene oxide into 100 mL of N, N-dimethylformamide, performing ultrasonic treatment at room temperature for 40 min, adding 0.1 g of 2, 4-dihydroxy benzophenone, heating to 70 ℃, performing magnetic stirring reaction for 4 h, then adding 3g of gamma-aminopropyltriethoxysilane modified white carbon black, and continuing to perform magnetic stirring reaction for 10 h; after the reaction is finished, performing centrifugal separation, fully washing the separated solid substance by 250 mL of absolute ethyl alcohol, and performing vacuum drying at 60 ℃ for 24 h to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide;
(2) placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 45 ℃ and plastifying for 3 min; adding 8g of paraffin, 4g of zinc oxide, 4.5g of N-phenyl-N' -cyclohexyl p-phenylenediamine, 37.5g of 2, 4-dihydroxy benzophenone and white carbon black chemically-bonded graphene oxide, 3.5g of an accelerator TBBS and 3g of dicumyl peroxide into the styrene butadiene rubber in sequence within 25 min; after the addition, continuously passing for 6 times, and slicing to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide/styrene butadiene rubber compound; and heating the rubber compound in an open mill to 70 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding at the molding temperature of 160 ℃, the molding pressure of 12 MPa and the molding time of 30 min to obtain the ultraviolet light aging resistant and wear resistant rain shoe.
Example 3
(1) Adding 0.1 g of carboxylated graphene oxide into 500 mL of thionyl chloride, heating to 100 ℃, and carrying out magnetic stirring reaction for 3 hours; after the reaction is finished, decompressing and distilling to remove excessive thionyl chloride, fully washing residues with anhydrous tetrahydrofuran, and drying in vacuum at 60 ℃ for 24 hours to prepare the acyl chloride graphene oxide; adding the prepared acyl chlorination graphene oxide into 500 mL of N, N-dimethylformamide, performing ultrasonic treatment at room temperature for 60 min, adding 0.5 g of 2, 4-dihydroxy benzophenone, heating to 80 ℃, performing magnetic stirring reaction for 2 h, then adding 5g of gamma-aminopropyltriethoxysilane modified white carbon black, and continuing to perform magnetic stirring reaction for 18 h; after the reaction is finished, performing centrifugal separation, fully washing the separated solid substance by using 500 mL of absolute ethyl alcohol, and performing vacuum drying at 60 ℃ for 24 h to prepare 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide;
(2) placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 50 ℃ and plastifying for 2 min; sequentially adding 10g of vaseline, 5g of zinc oxide, 6g of calcium-zinc composite stabilizer, 50g of 2, 4-dihydroxy benzophenone and white carbon black chemically-bonded graphene oxide, 5g of promoter DZ and 5g of benzoyl peroxide into the styrene butadiene rubber within 30 min; after the addition, continuously passing for 8 times, and performing sheet discharging to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide/styrene butadiene rubber compound; and heating the rubber compound in an open mill to 90 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 170 ℃, the molding pressure is 10 MPa, and the molding time is 20 min, so as to obtain the ultraviolet light aging resistant and wear resistant rain shoe.
Comparative example 1
Placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 40 ℃, and plastifying for 4 min; sequentially adding 6g of aromatic oil, 3g of stearic acid, 3g of N-phenyl-alpha-naphthylamine, 0.27g of 2, 4-dihydroxy benzophenone, 0.05g of graphene oxide, 24.7g of white carbon black, 2g of promoter CZ and 1g of N, N' -m-phenylene bismaleimide into the styrene butadiene rubber within 20 min; after the addition, continuously passing for 4 times, and slicing to obtain 2, 4-dihydroxy benzophenone/graphene oxide/white carbon black/styrene butadiene rubber compound; and heating the rubber compound in an open mill to 50 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 150 ℃, the molding pressure is 14 MPa, and the molding time is 40 min, so as to obtain a rain shoe finished product.
Comparative example 2
Placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 45 ℃ and plastifying for 3 min; adding 8g of paraffin, 4g of zinc oxide, 4.5g of N-phenyl-N' -cyclohexyl p-phenylenediamine, 1.2g of 2, 4-dihydroxy benzophenone, 0.24g of graphene oxide, 36.06g of white carbon black, 3.5g of an accelerator TBBS and 3g of dicumyl peroxide into the styrene butadiene rubber in sequence within 25 min; after the addition, continuously passing for 6 times, and slicing to obtain 2, 4-dihydroxy benzophenone/graphene oxide/white carbon black/styrene butadiene rubber compound; and heating the rubber compound to 70 ℃ in an open mill, and then putting the rubber compound into a rain shoe mold for vulcanization molding, wherein the molding temperature is 160 ℃, the molding pressure is 12 MPa, and the molding time is 30 min, so as to obtain a rain shoe finished product.
Comparative example 3
Placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 50 ℃ and plastifying for 2 min; sequentially adding 10g of vaseline, 5g of zinc oxide, 6g of calcium-zinc composite stabilizer, 4.5g of 2, 4-dihydroxy benzophenone, 0.9g of graphene oxide, 44.6g of white carbon black, 5g of accelerant DZ and 5g of benzoyl peroxide into the styrene butadiene rubber within 30 min; after the addition, continuously passing for 8 times, and performing sheet discharging to obtain 2, 4-dihydroxy benzophenone/graphene oxide/white carbon black/styrene butadiene rubber compound; and heating the rubber compound in an open mill to 90 ℃, and then putting the rubber compound in a rain boot mold for vulcanization molding, wherein the molding temperature is 170 ℃, the molding pressure is 10 MPa, and the molding time is 20 min, so as to obtain a rain boot finished product.
The rain boot materials prepared in the three groups of examples and the three groups of comparative examples are tested for tensile strength and elongation at break according to GB/T528-2The test results are shown in table 1.
Table 1 results of performance testing
From the test results of the three groups of examples, the ultraviolet aging resistance, the wear resistance and the mechanical property of the rain boot material in the three groups of examples are obviously improved compared with styrene butadiene rubber. It can be seen from the test results of the three comparative examples that although the contents of 2, 4-dihydroxybenzophenone, graphene oxide and white carbon black of the three comparative examples are the same as those of the respective examples, the ultraviolet light aging resistance, abrasion resistance and mechanical properties of the three comparative examples are inferior to those of the respective examples because they are directly added to styrene butadiene rubber and the dispersibility and stability after dispersion are poor. The ultraviolet absorbent and the white carbon black are chemically bonded on the surface of the graphene oxide to prepare the 2, 4-dihydroxy benzophenone and the white carbon black chemically bonded graphene oxide, and the graphene oxide is filled in the styrene butadiene rubber rain boot material, so that the ultraviolet aging resistance, the wear resistance and the mechanical property of the rain boot can be obviously improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of ultraviolet light aging resistant and wear resistant rain shoes is characterized in that: the method specifically comprises the following steps:
(1) adding 0.002-0.1 g of carboxylated graphene oxide into 10-500 mL of thionyl chloride, heating to 80-100 ℃, and carrying out magnetic stirring reaction for 3-6 h; after the reaction is finished, decompressing and distilling to remove excessive thionyl chloride, fully washing residues with anhydrous tetrahydrofuran, and drying in vacuum at 60 ℃ for 24 hours to prepare the acyl chloride graphene oxide; adding the prepared acylchlorination graphene oxide into 10-500 mL of N, N-dimethylformamide, performing ultrasonic treatment at room temperature for 20-60 min, adding 0.01-0.5 g of 2, 4-dihydroxy benzophenone, heating to 60-80 ℃, performing magnetic stirring reaction for 2-6 h, adding 1-5 g of gamma-aminopropyltriethoxysilane modified white carbon black, and continuing the magnetic stirring reaction for 4-18 h; after the reaction is finished, performing centrifugal separation, fully washing the separated solid matter with 100-500 mL of absolute ethyl alcohol, and performing vacuum drying at 60 ℃ for 24 hours to obtain 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide;
(2) placing 100g of styrene butadiene rubber in a double-roll open mill, controlling the roll temperature at 40-50 ℃, and plasticating for 2-4 min; sequentially adding 6-10 g of softener, 3-5 g of active agent, 3-6 g of anti-aging agent, 25-50 g of 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide, 2-5 g of promoter and 1-5 g of cross-linking agent into the styrene butadiene rubber within 20-30 min, continuously passing for 4-8 times, and discharging to obtain a 2, 4-dihydroxy benzophenone and white carbon black chemically bonded graphene oxide/styrene butadiene rubber mixed rubber; and heating the rubber compound in an open mill to 50-90 ℃, and then putting the rubber compound in a rain shoe mold for vulcanization molding, wherein the molding temperature is 150-170 ℃, the molding pressure is 10-14 MPa, and the molding time is 20-40 min, so as to obtain the ultraviolet light aging resistant and wear resistant rain shoe.
2. The method for preparing the ultraviolet light aging resistant and wear resistant rain shoes as claimed in claim 1, wherein the method comprises the following steps: the softening agent is aromatic oil, paraffin or vaseline.
3. The method for preparing the ultraviolet light aging resistant and wear resistant rain shoes as claimed in claim 1, wherein the method comprises the following steps: the active agent is zinc oxide or stearic acid.
4. The method for preparing the ultraviolet light aging resistant and wear resistant rain shoes as claimed in claim 1, wherein the method comprises the following steps: the anti-aging agent is N-phenyl-alpha-naphthylamine, N-phenyl-N' -cyclohexyl p-phenylenediamine or a calcium-zinc composite stabilizer.
5. The method for preparing the ultraviolet light aging resistant and wear resistant rain shoes as claimed in claim 1, wherein the method comprises the following steps: the accelerant is an accelerant 808, an accelerant CZ, an accelerant TBBS, an accelerant NOBS or an accelerant DZ.
6. The method for preparing the ultraviolet light aging resistant and wear resistant rain shoes as claimed in claim 1, wherein the method comprises the following steps: the cross-linking agent is N, N' -m-phenylene bismaleimide, dicumyl peroxide, sulfur, benzoyl peroxide or 2, 4-dichloro benzoyl peroxide.
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| CN104693546A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Preparation method of high-performance graphene oxide/solution polymerized styrene-butadiene rubber composite material |
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