CN112920477B - Rubber composite material and application thereof in sand suction rubber tube - Google Patents
Rubber composite material and application thereof in sand suction rubber tube Download PDFInfo
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- CN112920477B CN112920477B CN202110063569.2A CN202110063569A CN112920477B CN 112920477 B CN112920477 B CN 112920477B CN 202110063569 A CN202110063569 A CN 202110063569A CN 112920477 B CN112920477 B CN 112920477B
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- butadiene rubber
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 123
- 239000005060 rubber Substances 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 239000004576 sand Substances 0.000 title claims abstract description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 95
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 20
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008117 stearic acid Substances 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims 1
- 229920006978 SSBR Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000004594 Masterbatch (MB) Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002064 nanoplatelet Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- -1 acrylic graft-modified styrene-butadiene Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a rubber composite material and application thereof in a sand suction rubber tube, wherein the rubber composite material comprises the following raw materials in parts by weight: 35-45 parts of graphene oxide/styrene-butadiene rubber composite rubber, 85-95 parts of styrene-butadiene rubber, 5-15 parts of white carbon black, 1-5 parts of stearic acid, 1-5 parts of nano zinc oxide, 1-3 parts of adhesive, 1-3 parts of vulcanizing agent, 0.5-1 part of vulcanization accelerator and 1-3 parts of anti-aging agent; the graphene oxide/styrene-butadiene rubber composite rubber is obtained by mixing isocyanate functionalized graphene oxide and acrylic acid grafted modified styrene-butadiene rubber. The rubber composite material provided by the invention has the excellent performances of high wear resistance and high strength, and the wear resistance and the use performance of the rubber composite material in the sand suction rubber pipe are effectively ensured.
Description
Technical Field
The invention relates to the technical field of sand-absorbing rubber tubes, in particular to a rubber composite material and application thereof in sand-absorbing rubber tubes.
Background
People need to suck solid substances or granular materials such as ore sand, coal dust and the like in daily life or production. The mechanical equipment for carrying out the works is provided with a sand sucking pipe for sucking the granular materials, and the metal pipe is used as the sand sucking pipe originally, but the metal pipe is hard and cannot meet the condition of bending the pipe, and the sand sucking rubber pipe with flexibility is changed later. Because the use condition of the sand suction hose is harsh, the abrasion resistance of the sand suction hose is generally poor, the abrasion is very serious after the service time is long, and the sand suction hose is often required to be replaced.
Styrene-butadiene rubber is often used as a sand-absorbing rubber tube because of its relatively good heat aging and abrasion resistance. Considering the harsh working environment of the sand sucking rubber pipe for a long time, the abrasion resistance of the sand sucking rubber pipe is still insufficient. At present, a mechanical blending method is generally adopted in industrial production to introduce compounding agents such as filler into styrene-butadiene rubber products so as to achieve the performances of improving mechanical wear resistance and the like, but the mechanical blending method cannot achieve the states of high stripping, high dispersion and high interfacial force of the compounding agents such as filler in rubber, so that the excellent performance of the styrene-butadiene rubber is prevented from being exerted.
The graphene oxide is used as an intermediate product in the graphene preparation process by an oxidation-reduction method, has excellent mechanical properties, increases interlayer spacing due to the existence of oxygen-containing functional groups on the surface of the sheet, improves the compatibility between the sheet and rubber, and can greatly improve the hardness, modulus, stretching stress, wear resistance and the like of the rubber composite material by being used as a rubber reinforcing agent. However, as the mechanical blending method and the solution blending method are generally adopted for the compounding of the graphene oxide and the rubber material, the graphene oxide is difficult to peel off and uniformly disperse in the rubber matrix by the mechanical blending method, and the high shearing force can break up the graphene oxide sheets in the mechanical blending process; although the graphene oxide can be peeled off and uniformly dispersed by solution blending, the use of a large amount of organic solvents causes environmental pollution and is costly.
Therefore, how to improve the dispersion performance of the graphene oxide in the rubber product so as to exert the wear-resistant improving function of the graphene oxide to the maximum extent is of great significance in improving the wear-resistant service performance of the sand suction rubber tube.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a rubber composite material and application thereof in a sand suction rubber tube, wherein the rubber composite material has excellent performances of high wear resistance and high strength, and the wear resistance and the service performance of the rubber composite material in the sand suction rubber tube are effectively ensured.
The invention provides a rubber composite material, which comprises the following raw materials in parts by weight: 35-45 parts of graphene oxide/styrene-butadiene rubber composite rubber, 85-95 parts of styrene-butadiene rubber, 5-15 parts of white carbon black, 1-5 parts of stearic acid, 1-5 parts of nano zinc oxide, 1-3 parts of adhesive, 1-3 parts of vulcanizing agent, 0.5-1 part of vulcanization accelerator and 1-3 parts of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is obtained by mixing isocyanate functionalized graphene oxide and acrylic acid grafted modified styrene-butadiene rubber.
Preferably, the isocyanate functional graphene oxide is obtained by condensation reaction of graphene oxide and diisocyanate.
Preferably, the diisocyanate is terephthalyl diisocyanate;
preferably, the mass ratio of the graphene oxide to the diisocyanate is 1:6-10.
Preferably, the acrylic acid graft modified styrene-butadiene rubber is obtained by graft polymerizing solution polymerized styrene-butadiene rubber and acrylic acid;
preferably, the mass ratio of the solution polymerized styrene-butadiene rubber to the acrylic acid is 1:0.2-0.3.
Preferably, the mass ratio of the isocyanate functional graphene oxide to the acrylic acid graft modified styrene-butadiene rubber is 1:0.3-0.5.
Preferably, the vulcanizing agent is sulfur and the vulcanization accelerator is accelerator CZ.
Preferably, the adhesive is adhesive RC, and the antioxidant is a p-phenylenediamine antioxidant, preferably an antioxidant 4020.
The invention provides a preparation method of a rubber composite material, which comprises the following steps: mixing the graphene oxide/styrene-butadiene rubber composite rubber, styrene-butadiene rubber, white carbon black, stearic acid, nano zinc oxide, an adhesive, a vulcanizing agent, a vulcanization accelerator and an anti-aging agent.
The invention also provides application of the rubber composite material in a sand suction hose.
Preferably, the sand absorbing rubber tube comprises the rubber composite material and a framework material embedded in the rubber composite material.
According to the invention, the isocyanate functionalized graphene oxide and the acrylic acid graft modified styrene-butadiene rubber are mixed to obtain the graphene oxide/styrene-butadiene rubber composite rubber, and as the isocyanate groups are grafted on the surface of the isocyanate functionalized graphene oxide tube and the carboxylic acid groups are grafted on the surface of the acrylic acid graft modified styrene-butadiene rubber, when the isocyanate groups and the carboxylic acid groups are mixed, the isocyanate groups and the carboxylic acid groups can form an adsorption reaction, so that firm combination can be formed between the isocyanate functionalized graphene oxide and the acrylic acid graft modified styrene-butadiene rubber, thereby ensuring good dispersibility and affinity of graphene oxide in styrene-butadiene rubber, ensuring uniform dispersion of graphene oxide in rubber products, and further showing better reinforcing effect in the rubber products. The rubber composite material finally obtained by the invention shows obviously excellent wear resistance and high strength.
Detailed Description
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
The invention provides a rubber composite material, which comprises the following raw materials in parts by weight: 35-45 parts of graphene oxide/styrene-butadiene rubber composite rubber, 85-95 parts of styrene-butadiene rubber, 5-15 parts of white carbon black, 1-5 parts of stearic acid, 1-5 parts of nano zinc oxide, 1-3 parts of adhesive, 1-3 parts of vulcanizing agent, 0.5-1 part of vulcanization accelerator and 1-3 parts of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is obtained by mixing isocyanate functionalized graphene oxide and acrylic acid grafted modified styrene-butadiene rubber.
In the formula, the graphene oxide/styrene-butadiene rubber composite rubber is selected as the pre-dispersion master batch of the graphene oxide, so that the graphene oxide can be uniformly dispersed in the subsequent composite material, the defect of poor dispersibility caused by direct mechanical mixing of the graphene oxide and the styrene-butadiene rubber in the prior art is overcome, and the rubber composite material with improved wear resistance and strength performance is finally obtained.
Meanwhile, the rubber material obtained by the formula can have stronger adhesive force with a framework material to ensure stable adhesive effect, so that the rubber material can be effectively used for preparing the wear-resistant sand-absorbing rubber tube.
In a preferred embodiment of the present invention, the acrylic graft-modified styrene-butadiene rubber is obtained by graft-polymerizing solution-polymerized styrene-butadiene rubber with acrylic acid, and the acrylic graft-modified styrene-butadiene rubber has an acrylic acid graft ratio of 1.4 to 2.1wt%.
The acrylic acid grafted modified styrene-butadiene rubber with the grafting ratio content can not only provide an adsorption reaction of a sufficient amount of carboxylic acid groups on isocyanate functionalized graphene oxide, but also ensure that the modified styrene-butadiene rubber cannot be too polarized due to excessive grafting reaction to influence the compatibility between the follow-up rubber and the matrix rubber.
In a preferred further embodiment of the present invention, the isocyanate functionalized graphene oxide is obtained by condensation reaction of graphene oxide with a diisocyanate.
The isocyanate functional graphene oxide obtained by the reaction has the following structural schematic:
in order to more clearly describe the rubber composite materials provided by the embodiments of the present invention in detail, the following description will be made with reference to specific embodiments.
Example 1
The rubber composite material comprises the following raw materials in parts by weight: 40 parts of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts of solution polymerized styrene-butadiene rubber SSBR, 10 parts of white carbon black, 3 parts of stearic acid, 3 parts of nano zinc oxide, 2 parts of adhesive RC, 2 parts of sulfur, 0.7 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid graft modified styrene-butadiene rubber and isocyanate functional graphene oxide with the mass ratio of 0.4:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the isocyanate functional graphene oxide is prepared by the following method: adding graphene oxide GO (obtained by synthesizing graphene nanoplatelets through a Hummers method) into anhydrous DMF according to the mass-volume ratio of 1g to 20mL, introducing nitrogen to remove air, performing ultrasonic dispersion uniformly, adding terephthalyl diisocyanate PPDI with the mass of 8 times of graphene oxide, stirring at room temperature for reaction for 24 hours, filtering, and sequentially using DMF and CH 2 Cl 2 Washing twice, vacuum drying at 60 ℃, and grinding to obtain isocyanate functional graphene oxide;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 5% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 25% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, carrying out heat preservation and stirring reaction for 4 hours, adding absolute ethyl alcohol after finishing the reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 1.8%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 40 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 10 parts by weight of white carbon black, 3 parts by weight of stearic acid, 3 parts by weight of nano zinc oxide, 2 parts by weight of adhesive RC and 2 parts by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 2 parts by weight of sulfur and 0.7 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final mixed rubber, namely the rubber composite material.
Example 2
The rubber composite material comprises the following raw materials in parts by weight: 35 parts of graphene oxide/styrene-butadiene rubber composite rubber, 95 parts of solution polymerized styrene-butadiene rubber SSBR, 5 parts of white carbon black, 5 parts of stearic acid, 1 part of nano zinc oxide, 3 parts of adhesive RC, 1 part of sulfur, 1 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid graft modified styrene-butadiene rubber and isocyanate functional graphene oxide with the mass ratio of 0.3:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the isocyanate functional graphene oxide is prepared by the following method: adding graphene oxide GO (obtained by synthesizing graphene nanoplatelets through a Hummers method) into anhydrous DMF according to the mass-volume ratio of 1g to 20mL, introducing nitrogen to remove air, performing ultrasonic dispersion uniformly, adding terephthalyl diisocyanate PPDI with the mass of 6 times of graphene oxide, stirring at room temperature for reaction for 24 hours, filtering, and sequentially using DMF and CH 2 Cl 2 Washing twice, vacuum drying at 60 ℃, and grinding to obtain isocyanate functional graphene oxide;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 5% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 30% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, carrying out heat preservation and stirring reaction for 4 hours, adding absolute ethyl alcohol after finishing the reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 2.1%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 35 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 95 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 5 parts by weight of white carbon black, 5 parts by weight of stearic acid, 1 part by weight of nano zinc oxide, 3 parts by weight of adhesive RC and 1 part by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 1 part by weight of sulfur and 1 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final rubber, namely the rubber composite material.
Example 3
The rubber composite material comprises the following raw materials in parts by weight: 45 parts of graphene oxide/styrene-butadiene rubber composite rubber, 85 parts of solution polymerized styrene-butadiene rubber SSBR, 15 parts of white carbon black, 1 part of stearic acid, 5 parts of nano zinc oxide, 1 part of adhesive RC, 3 parts of sulfur, 0.5 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid graft modified styrene-butadiene rubber and isocyanate functional graphene oxide with the mass ratio of 0.5:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the isocyanate functional graphene oxide is prepared by the following method: adding graphene oxide GO (obtained by synthesizing graphene nanoplatelets through a Hummers method) into anhydrous DMF according to the mass-volume ratio of 1g to 20mL, introducing nitrogen to remove air, performing ultrasonic dispersion uniformly, adding terephthalyl diisocyanate PPDI with the mass of 10 times of graphene oxide, stirring at room temperature for reaction for 24 hours, filtering, and sequentially using DMF and CH 2 Cl 2 Washing twice, vacuum drying at 60 ℃, and grinding to obtain isocyanate functional graphene oxide;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 5% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 20% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, preserving heat, stirring for 4 hours, adding absolute ethyl alcohol after finishing reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 1.4%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 45 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 85 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 15 parts by weight of white carbon black, 1 part by weight of stearic acid, 5 parts by weight of nano zinc oxide, 1 part by weight of adhesive RC and 3 parts by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 3 parts by weight of sulfur and 0.5 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final mixed rubber, namely the rubber composite material.
Example 4
The rubber composite material comprises the following raw materials in parts by weight: 40 parts of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts of solution polymerized styrene-butadiene rubber SSBR, 10 parts of white carbon black, 3 parts of stearic acid, 3 parts of nano zinc oxide, 2 parts of adhesive RC, 2 parts of sulfur, 0.7 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid graft modified styrene-butadiene rubber and isocyanate functional graphene oxide with the mass ratio of 0.4:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the isocyanate functional graphene oxide is prepared by the following method: adding graphene oxide GO (obtained by synthesizing graphene nanoplatelets through a Hummers method) into anhydrous DMF according to the mass-volume ratio of 1g to 20mL, introducing nitrogen to remove air, performing ultrasonic dispersion uniformly, adding terephthalyl diisocyanate PPDI with the mass of 8 times of graphene oxide, stirring at room temperature for reaction for 24 hours, filtering, and sequentially using DMF and CH 2 Cl 2 Washing twice, vacuum drying at 60 ℃, and grinding to obtain isocyanate functionalized graphene oxide;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 6% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 35% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, carrying out heat preservation and stirring reaction for 4 hours, adding absolute ethyl alcohol after finishing the reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 2.3%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 40 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 10 parts by weight of white carbon black, 3 parts by weight of stearic acid, 3 parts by weight of nano zinc oxide, 2 parts by weight of adhesive RC and 2 parts by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 2 parts by weight of sulfur and 0.7 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final mixed rubber, namely the rubber composite material.
Example 5
The rubber composite material comprises the following raw materials in parts by weight: 40 parts of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts of solution polymerized styrene-butadiene rubber SSBR, 10 parts of white carbon black, 3 parts of stearic acid, 3 parts of nano zinc oxide, 2 parts of adhesive RC, 2 parts of sulfur, 0.7 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid graft modified styrene-butadiene rubber and isocyanate functional graphene oxide with the mass ratio of 0.4:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the isocyanate functional graphene oxide is prepared by the following method: adding graphene oxide GO (obtained by synthesizing graphene nanoplatelets through a Hummers method) into anhydrous DMF according to the mass-volume ratio of 1g to 20mL, introducing nitrogen to remove air, performing ultrasonic dispersion uniformly, adding terephthalyl diisocyanate PPDI with the mass of 8 times of graphene oxide, stirring at room temperature for reaction for 24 hours, filtering, and sequentially using DMF and CH 2 Cl 2 Washing twice, vacuum drying at 60 ℃, and grinding to obtain isocyanate functionalized graphene oxide;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 5% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 15% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, carrying out heat preservation and stirring reaction for 4 hours, adding absolute ethyl alcohol after finishing the reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 1.1%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 40 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 10 parts by weight of white carbon black, 3 parts by weight of stearic acid, 3 parts by weight of nano zinc oxide, 2 parts by weight of adhesive RC and 2 parts by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 2 parts by weight of sulfur and 0.7 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final mixed rubber, namely the rubber composite material.
Comparative example 1
The rubber composite material comprises the following raw materials in parts by weight: 40 parts of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts of solution polymerized styrene-butadiene rubber SSBR, 10 parts of white carbon black, 3 parts of stearic acid, 3 parts of nano zinc oxide, 2 parts of adhesive RC, 2 parts of sulfur, 0.7 part of promoter CZ and 4020 part of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is prepared by adding acrylic acid grafting modified styrene-butadiene rubber and graphene oxide with the mass ratio of 0.4:1 into an internal mixer, and mixing for 6min under the conditions that the roller temperature is 40 ℃ and the rotor rotating speed is 80 rpm;
the graphene oxide GO is obtained by synthesizing graphene nano-platelets through a Hummers method;
the acrylic acid grafting modified styrene-butadiene rubber is prepared by the following method: adding solution polymerized styrene-butadiene rubber SSBR into cyclohexane according to the weight-volume ratio of 1g to 10mL, dissolving, adding an initiator azodiisoheptonitrile accounting for 5% of the mass of the solution polymerized styrene-butadiene rubber SSBR and monomer acrylic acid accounting for 25% of the mass of the solution polymerized styrene-butadiene rubber SSBR, heating to 70 ℃ under the protection of nitrogen, carrying out heat preservation and stirring reaction for 4 hours, adding absolute ethyl alcohol after finishing the reaction to precipitate a polymer, filtering, drying, extracting with absolute ethyl alcohol for 12 hours, and drying to obtain the acrylic acid grafted modified styrene-butadiene rubber (the grafting rate is 1.8%).
The preparation method of the rubber composite material comprises the following steps:
(1) Adding 40 parts by weight of graphene oxide/styrene-butadiene rubber composite rubber, 90 parts by weight of solution polymerized styrene-butadiene rubber SSBR, 10 parts by weight of white carbon black, 3 parts by weight of stearic acid, 3 parts by weight of nano zinc oxide, 2 parts by weight of adhesive RC and 2 parts by weight of anti-aging agent 4020 into an internal mixer, mixing for 10min at a roller temperature of 40 ℃ and a rotor rotating speed of 80rpm, cooling to room temperature after rubber discharge, and standing for 24h to obtain mixed master batch;
(2) And adding the mixed master batch, 2 parts by weight of sulfur and 0.7 part by weight of accelerator CZ into an open mill, and carrying out sheet discharging after 6 times of thin pass to obtain final mixed rubber, namely the rubber composite material.
The rubber composite materials obtained in the examples and the comparative examples are firstly parked for 24 hours at normal temperature, then are reworked on an open mill, and finally vulcanized for 30 minutes by using a die under the conditions of 160 ℃ and 10MPa pressure to obtain vulcanized rubber samples, and the detection results of the mechanical properties and the wear resistance are shown in the following table 1:
tensile properties: the tensile strength test is carried out according to the national standard GB/T528-2009 "determination of tensile stress and Strain properties of vulcanized rubber or thermoplastic rubber".
Abrasion performance: abrasion test was carried out according to the national standard GB/T1689-1998 abrasion resistance measurement of vulcanized rubber (with an Aldrich abrasion machine).
Table 1 results of performance test after vulcanization of rubber composites obtained in examples and comparative examples
As can be seen from the above table, the rubber composite material of the invention has excellent mechanical properties and wear resistance when being used for preparing the wear-resistant sand-absorbing rubber tube.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The rubber composite material is characterized by comprising the following raw materials in parts by weight: 35-45 parts of graphene oxide/styrene-butadiene rubber composite rubber, 85-95 parts of styrene-butadiene rubber, 5-15 parts of white carbon black, 1-5 parts of stearic acid, 1-5 parts of nano zinc oxide, 1-3 parts of adhesive, 1-3 parts of vulcanizing agent, 0.5-1 part of vulcanization accelerator and 1-3 parts of anti-aging agent;
the graphene oxide/styrene-butadiene rubber composite rubber is obtained by mixing isocyanate functionalized graphene oxide and acrylic acid grafted modified styrene-butadiene rubber;
the acrylic acid grafted modified styrene-butadiene rubber is obtained by graft polymerization of solution polymerized styrene-butadiene rubber and acrylic acid, and the mass ratio of the solution polymerized styrene-butadiene rubber to the acrylic acid is 1:0.2-0.3;
the mass ratio of the isocyanate functional graphene oxide to the acrylic acid grafted modified styrene-butadiene rubber is 1:0.3-0.5.
2. The rubber composite according to claim 1, wherein the isocyanate functionalized graphene oxide is obtained by a condensation reaction of graphene oxide with a diisocyanate.
3. The rubber composite of claim 2, wherein the diisocyanate is terephthal-diisocyanate.
4. The rubber composite according to claim 2, wherein the mass ratio of graphene oxide to diisocyanate is 1:6-10.
5. The rubber composite according to any one of claims 1 to 4, wherein the vulcanizing agent is sulfur and the vulcanization accelerator is accelerator CZ.
6. The rubber composite according to any one of claims 1 to 4, wherein the adhesive is adhesive RC and the antioxidant is a p-phenylenediamine type antioxidant.
7. The rubber composite of claim 6, wherein the anti-aging agent is an anti-aging agent 4020.
8. A method of making a rubber composite according to any one of claims 1 to 7, comprising: mixing the graphene oxide/styrene-butadiene rubber composite rubber, styrene-butadiene rubber, white carbon black, stearic acid, nano zinc oxide, an adhesive, a vulcanizing agent, a vulcanization accelerator and an anti-aging agent.
9. Use of a rubber composite according to any one of claims 1 to 7 in a sand absorbing hose.
10. The use of a rubber composite according to claim 9 in a sand absorbing hose, wherein the sand absorbing hose comprises the rubber composite and a matrix material embedded in the rubber composite.
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| CN208041400U (en) * | 2018-01-22 | 2018-11-02 | 广州胶管厂有限公司 | A kind of flaring Type B sand-suction hose facilitating installation |
| CN109422932A (en) * | 2017-08-27 | 2019-03-05 | 李波 | A kind of sand blast rubber hose |
| CN111303502A (en) * | 2020-03-16 | 2020-06-19 | 泉州市泉石通智能科技有限公司 | Modified graphene oxide/styrene butadiene rubber composite material and preparation method thereof |
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| CN109422932A (en) * | 2017-08-27 | 2019-03-05 | 李波 | A kind of sand blast rubber hose |
| CN208041400U (en) * | 2018-01-22 | 2018-11-02 | 广州胶管厂有限公司 | A kind of flaring Type B sand-suction hose facilitating installation |
| CN111303502A (en) * | 2020-03-16 | 2020-06-19 | 泉州市泉石通智能科技有限公司 | Modified graphene oxide/styrene butadiene rubber composite material and preparation method thereof |
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