CN112980217A - Modified GO-SiO2Preparation method of composite filler and application of composite filler in rubber - Google Patents
Modified GO-SiO2Preparation method of composite filler and application of composite filler in rubber Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 239000000945 filler Substances 0.000 title claims abstract description 52
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 62
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 62
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 62
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 62
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 20
- 235000019353 potassium silicate Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- 239000010692 aromatic oil Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 9
- 239000004111 Potassium silicate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 8
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 229920006978 SSBR Polymers 0.000 claims 2
- 238000005086 pumping Methods 0.000 claims 2
- 230000003712 anti-aging effect Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000012763 reinforcing filler Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
The invention belongs to the technical field of nano composite materials, and particularly relates to modified GO-SiO2Composite fillerThe invention provides a method for constructing modified Graphene Oxide (GO) -silicon dioxide (SiO)2) The composite filler solves the problems of GO and SiO2Poor dispersion effect in rubber and easy agglomeration, and endows the composite filler with anti-aging performance by modified GO. Firstly, modifying GO in one step by using an amino modifier through a hydrothermal method, wherein the modified GO is in a three-dimensional hole structure; then the silicon source is used for leading SiO to be processed by an in-situ growth method2The particles are deposited and interpenetrated on the surface of the modified GO and in the holes; preparing novel modified GO-SiO2Composite filler; the problem of agglomeration of the reinforcing filler can be effectively solved, the interaction between the filler and the filler is reduced, and the mechanical property and the ageing resistance of the rubber are improved.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to modified GO-SiO2A preparation method of the composite filler and application of the composite filler in rubber.
Background
Graphene is a carbonaceous material with a monolayer two-dimensional honeycomb lattice structure formed by tightly packing sp2 hybridized and connected carbon atoms. Graphene has an infinitely repeated periodic structure in a plane, has a nanoscale in a direction perpendicular to the plane, and can be regarded as a nano material with a macroscopic size. The graphene has high specific surface area, large aspect ratio, high modulus and good solvent dispersibility, and is a rubber reinforced filler with high potential. GO and graphene have similar structures and performances, a plurality of surface groups and low price, and become excellent fillers of polymers such as rubber and plastic, but GO is easy to cause the reduction of rubber performance in a polymer matrix due to aggregation.
SiO2As a reinforcing agent of the traditional rubber, the rubber has the characteristics of low rolling resistance and good wet skid resistance. But at the same time SiO2Dispersion in rubber is also a difficult problem because of the strong tendency to agglomerate due to the small particle size.
Disclosure of Invention
The invention aims to develop a modified GO-SiO2Composite filler, with emphasis on solving GO and SiO2Difficult dispersion in rubber, and at the same time, the reinforcing filler has an anti-ageing effect. According to the invention, the GO is modified into a three-dimensional pore structure by using a modifier, so that the specific surface area is increased; construction of modified GO-SiO by in-situ growth2Sol to SiO2Load and interpenetration are in modified GO hole structure, and the modifier endows GO with anti-aging performance, so that GO and SiO are prevented from being added into rubber to achieve a reinforcing effect2Agglomeration in a rubber matrix.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a modified GO-SiO2The preparation method of the composite filler comprises the following steps:
the method comprises the following steps: preparation of modified GO: firstly, mixing GO and water in a mass ratio of 1: (40-60) mixing to obtain a GO aqueous solution, and putting the GO aqueous solution into an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, and the ultrasonic time is 25-35min to obtain a GO aqueous solution with the concentration of 16-25 mg/ml; and then adding a modifier and ammonia water with the pH value of 10-11 into the GO aqueous solution, wherein the volume ratio of the modifier to the ammonia water to the GO aqueous solution is (5-7): (1-3): 25; magnetically stirring the mixture for 20min at the temperature of between 25 and 30 ℃, adding the mixture into a hydrothermal reaction kettle, reacting the mixture for 8 to 12h at the temperature of between 170 and 190 ℃, and cooling the mixture; and washing with deionized water for 3-5 times to remove unreacted modifier, and freeze-drying for 48h to obtain the modified GO.
Step two: preparation of modified GO-SiO2Composite filling: firstly, mixing the modified GO obtained in the step one with deionized water according to the mass ratio of 1: 1200, mixing to obtain a modified GO aqueous solution, placing the modified GO aqueous solution in an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, and the ultrasonic time is ultrasonicThe time is 25-35min, and modified GO aqueous solution with the concentration of 0.83mg/ml is prepared; and then, mixing a silicon source and the modified GO dispersion liquid according to the mass ratio of 1: 5, mixing to obtain a mixed solution, and then adding a surfactant, wherein the mass ratio of the surfactant to the modified GO dispersion liquid is 1: 500, mixing and pre-stirring for 20-30min, simultaneously keeping the constant temperature of the mixed solution at 0-5 ℃, and then adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the silicon source to the dilute hydrochloric acid is 1: 2.5, stirring while dropwise adding for 4-6 h to form a gel substance to obtain the modified GO-SiO2Gelling; finally, standing and aging the obtained gel for 10-12 h, then performing vacuum filtration by using a suction filtration machine, and washing with deionized water for 5-10 times; drying the mixture in a blast drying oven at 80 ℃ for 5-8 h, and further crushing the dried powder to obtain modified GO-SiO2And (4) composite filling.
The modifier adopted in the first step of the invention is one or more of p-phenylenediamine, triethylene tetramine and tetraethylene pentamine.
The surfactant used in the second step of the invention is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and sodium dodecyl sulfonate.
The silicon source adopted in the second step of the invention is one or more of tetraethyl orthosilicate, sodium silicate water glass and potassium silicate water glass.
Modified GO-SiO2The application of the composite filler in the SSBR comprises the following raw materials in parts by mass: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO230 to 50phr of composite filler.
Modified GO-SiO2The application of the/SSBR composite material in the SSBR of the solution polymerized styrene-butadiene rubber comprises the following steps: the temperature of the torque rheometer is set to be 110 ℃, and the rotating speed of the rotor is 70 r/min; according to the formula, SSBR, stearic acid, zinc oxide and modified GO-SiO are sequentially added2Carrying out one-stage banburying on the composite filler and the environment-friendly aromatic oil, wherein the banburying time is 7min, the rubber discharging temperature is 140 ℃, and cooling for 4 h; then adding a scorch retarder, accelerators CZ, DM and sulfur into an open mill with the roll temperature of 60 DEG CPerforming two-stage mixing with sulfur, adjusting roller spacing to 0.8-1.0mm, making triangular bag, passing through for 7-8 times, adjusting roller spacing to 2-3mm, placing at room temperature for 12-24h, vulcanizing at 170 deg.C under 12MPa for 10min, and modifying GO-SiO2The amount of the composite filler was 45 phr.
Compared with the prior art, the invention provides a modified GO-SiO2The preparation method of the composite filler and the application of the composite filler in rubber have the following beneficial effects: the invention provides modified GO-SiO2The preparation method of the composite filler has simple system and process and is easy to expand. Modified GO-SiO2The preparation of the composite filler takes a modified GO aqueous solution and a silicon source as precursors, and the ratio of the silicon source to the GO, the type of a dispersing agent, the concentration of the GO aqueous solution and the like are controlled through the selection of a GO modifier, so that the porous three-dimensional nano carbon material with the nanometer size, the large specific surface area and the high porosity is prepared. The composite filler can be used as an excellent material to be applied to rubber reinforcement; in addition, the anti-aging modification of GO also enables the rubber to replace an anti-aging agent.
Drawings
FIG. 1 is a modified GO-SiO solid solution provided by the invention2Tensile profile of the solution polymerized styrene butadiene rubber composite when 45phr of composite particles was filled.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
Example 1
The method comprises the following steps: preparation of modified GO: firstly, GO and water are mixed in a mass ratio of 1: 50 to obtain a GO aqueous solution, and putting the GO aqueous solution into an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30min to obtain a GO aqueous solution with the concentration of 20 mg/ml; and then adding a modifier Tetraethylenepentamine (TEPA) and ammonia water with the pH value of 10-11 into the GO aqueous solution, wherein the volume ratio of TEPA to ammonia water to GO aqueous solution is 6: 2: 25; magnetically stirring at 25 deg.C for 20min, adding into hydrothermal reaction kettle, reacting at 180 deg.C for 10 hr, and cooling; and washing with deionized water for 5 times to remove unreacted TEPA, and freeze-drying for 48h to obtain the modified GO.
Step two: preparation of modified GO-SiO2Composite filling: firstly, mixing the modified GO obtained in the step one with deionized water according to the mass ratio of 1: 1200, obtaining a modified GO aqueous solution after mixing, and placing the modified GO aqueous solution in an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30min, so as to obtain the modified GO aqueous solution with the concentration of 0.83 mg/ml; then, mixing potassium silicate water glass with a modulus of 3.3 and the modified GO dispersion liquid in a mass ratio of 1: 5, mixing to obtain a mixed solution, and adding sodium dodecyl benzene sulfonate (LAS), wherein the mass ratio of the LAS to the modified GO dispersion liquid is 1: 500, mixing and pre-stirring for 25min, simultaneously keeping the constant temperature of the mixed solution at 0-5 ℃, adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the potassium silicate water glass to the dilute hydrochloric acid is 1: 2.5, stirring while dripping for 5h to form a gel-like substance to obtain the modified GO-SiO2Gelling; finally, standing and aging the obtained gel for 10 hours, then performing vacuum filtration by using a suction filtration machine, and washing the gel for 5 times by using deionized water; drying in a blast drying oven at 80 ℃ for 5h, and further crushing the dried powder to obtain modified GO-SiO2And (4) composite filling.
Modified GO-SiO2Application of composite filler in SSBR (styrene butadiene rubber) prepared by taking modified GO-SiO2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO230phr of composite filler.
The temperature of the torque rheometer is set to be 110 ℃, and the rotating speed of the rotor is 70 r/min; according to the formula, SSBR, stearic acid, zinc oxide and modified GO-SiO are sequentially added2Carrying out one-stage banburying on the composite filler and the environment-friendly aromatic oil, wherein the banburying time is 7min, the rubber discharging temperature is 140 ℃, and cooling for 4 h; adding an anti-coking agent, an accelerant CZ, DM and sulfur on an open mill with a roll temperature of 60 ℃ for two-stage mixing, adjusting the roll spacing to be 0.8-1.0mm, packaging in a triangular bag, passing through for 7-8 times, adjusting the roll spacing to be 2-3mm, discharging, standing at room temperature for 12-24h, and standing at 170 ℃ under 12MPa × 10And vulcanizing under the min condition.
Example 2
The modified GO-SiO prepared in example 1 above was taken2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO235phr of composite material.
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
Example 3
The modified GO-SiO prepared in example 1 above was taken2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO2Composite 40 phr.
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
Example 4
The modified GO-SiO prepared in example 1 above was taken2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO2Composite 45 phr.
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
Example 5
The modified GO-SiO prepared in example 1 above was taken2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO250phr of composite material.
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
Comparative example 1
Preparation of GO-SiO2Composite filling: (1) mixing GO and deionized water in a mass ratio of 1: 1200, obtaining GO aqueous solution after mixing, and placing the GO aqueous solution in an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30min, so as to obtain the GO aqueous solution with the concentration of 0.83 mg/ml; (2) mixing potassium silicate water glass with a modulus of 3.3 and GO dispersion liquid according to a mass ratio of 1: 5 mixing to obtain a mixed solution, and then adding LAS, wherein the mass ratio of LAS to GO dispersion liquid is 1: 500, mixing and pre-stirring for 25min, simultaneously keeping the constant temperature of the mixed solution at 0-5 ℃, adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the potassium silicate water glass to the dilute hydrochloric acid is 1: 2.5, stirring while dripping for 5h to form a gel substance to obtain GO-SiO2Gelling; (3) standing and aging the obtained gel for 10h, then performing vacuum filtration by using a suction filtration machine, and washing with deionized water for 5 times; drying in a blast drying oven at 80 ℃ for 5h, and further crushing the dried powder to obtain GO-SiO2And (4) composite filling.
GO-SiO2Application of composite filler in SSBR (solid State biofilm reactor), namely GO-SiO prepared by the method2The composite filler comprises the following rubber experimental formula and parts by weight: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent, 0.1phr of GO-SiO2Composite 45 phr.
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
Comparative example 2
Preparation of SiO2: (1) mixing potassium silicate water glass with a modulus of 3.3 and deionized water according to a mass ratio of 1: 5, mixing to obtain a mixed solution, and then adding LAS, wherein the mass ratio of LAS to deionized water is 1: 500, mixing and pre-stirring for 25min, simultaneously keeping the constant temperature of the mixed solution at 0-5 ℃, adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the potassium silicate water glass to the dilute hydrochloric acid is 1: 2.5 stirring while dropping for 5h to form a gelTo obtain SiO2Gelling; (2) standing and aging the obtained gel for 10h, then performing vacuum filtration by using a suction filtration machine, and washing with deionized water for 5 times; drying in a forced air drying oven at 80 ℃ for 5h, and further crushing the dried powder to obtain SiO2And (4) filling.
SiO2Application in SSBR (single layer vacuum distillation) by taking the SiO prepared by the method2The rubber experiment formula and the parts by mass are as follows: 100phr of SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.5 phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent, 0.1phr of SiO245phr。
According to the above formulation, a vulcanizate was prepared and tested for various basic properties according to the vulcanizate preparation method of example 1.
The mechanical property test of comparative examples 1-2 and examples 1-5 was carried out, and the test results are shown in Table 1:
TABLE 1 mechanical Properties of the rubber composites
As can be seen from Table 1, with the modification of GO-SiO2The tensile strength, elongation at break and tear strength of the SSBR composite materials of examples 1-5 increased with the increase of the number of filler parts, and the shore a hardness increased gradually. The improvement of the mechanical property is mainly due to the modified GO-SiO2The composite filler reacts with the rubber matrix to form better bonding force; and the decline is mainly due to the following modification of GO-SiO2The increase of the filling amount of the composite filler gradually reduces the dispersity in rubber, so that stress concentration and interface separation are easily generated in a performance test, and the external force resistance of the rubber is reduced under continuous load. When modified GO-SiO2When the composite material reaches 45phr, namely, when the composite material is obtained in example 4, the comprehensive mechanical property of the SSBR composite material is better. From the mechanical properties of comparative examples 1-2 and example 4, it can be seen that the modified GO-SiO2The mechanical property of the composite material reinforced rubber is obviously improved mainly due to the modified GO-SiO2Surface jointThe branched hydrophobic groups improve their dispersibility in rubber and compare to SiO2And GO-SiO2For the composite material, the unique reticular hole structure is combined with the rubber matrix more tightly, thereby improving the mechanical property of the rubber.
The aging resistance of comparative examples 1-2 and examples 1-5 was tested, and the test results are shown in Table 2:
TABLE 2 ageing resistance of rubber composites
Note: negative values indicate a decrease in the value after aging and positive values indicate an increase.
As can be seen from Table 2, the Shore A hardness, tensile strength and tear strength of the rubbers of examples 1-5 after thermo-oxidative aging tests (70 ℃ C.. times.72 h) all tended to increase and decrease with increasing filler fraction, indicating that the modified GO-SiO2The addition of the composite filler can improve the ageing resistance of the rubber composite material. Under the condition of thermo-oxidative aging, free radicals generated by rubber are captured by primary amine groups and secondary amine groups on the surface of the modified GO to initiate chain termination, so that the anti-aging effect is achieved; the trend is reduced due to the modified GO-SiO2The composite filler is agglomerated in rubber due to excessive addition amount, so that the filler is separated from a rubber interface, and the anti-aging effect is reduced; taken together, the best anti-aging effect is seen in example 4, namely modified GO-SiO2The composite filler worked the most well when filled at 45 phr. Comparative examples 1-2 compared to example 4, comparative examples 1-2 did not have the same mechanical properties as example 4 after aging, which is mainly SiO2And GO-SiO2The composite filler mainly plays a reinforcing effect in a rubber matrix, and the modified GO-SiO2The composite filler has a reinforcing effect, and the modified GO surface grafted groups can have an anti-aging effect and can keep good mechanical properties.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. Modified GO-SiO2The preparation method of the composite filler is characterized by comprising the following steps:
the method comprises the following steps: preparation of modified GO: firstly, GO and water are mixed in a mass ratio of 1: (40-60) mixing to obtain a GO aqueous solution, and putting the GO aqueous solution into an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, and the ultrasonic time is 25-35min to obtain the GO aqueous solution with the concentration of 16-25 mg/ml; and then adding a modifier and ammonia water with the pH = 10-11 into the GO aqueous solution, wherein the volume ratio of the modifier to the ammonia water to the GO aqueous solution is (5-7): (1-3): 25; magnetically stirring for 20min at 25-30 ℃, adding into a hydrothermal reaction kettle, reacting for 8-12 h at 170-190 ℃, and cooling; washing with deionized water for 3-5 times to remove unreacted modifier, and freeze-drying for 48h to obtain modified GO;
step two: preparation of modified GO-SiO2Composite filling: firstly, mixing the modified GO obtained in the step one with deionized water according to the mass ratio of 1: 1200, obtaining a modified GO aqueous solution after mixing, and placing the modified GO aqueous solution in an ultrasonic cleaning machine for ultrasonic dispersion, wherein the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, and the ultrasonic time is 25-35min, so as to obtain a modified GO aqueous solution with the concentration of 0.83 mg/ml; and then, mixing a silicon source and the modified GO dispersion liquid according to the mass ratio of 1: 5, mixing to obtain a mixed solution, and then adding a surfactant, wherein the mass ratio of the surfactant to the modified GO dispersion liquid is 1: 500, mixing and pre-stirring for 20-30min, simultaneously keeping the constant temperature of the mixed solution at 0-5 ℃, and then adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the silicon source to the dilute hydrochloric acid is 1: 2.5, stirring while dropwise adding for 4-6 h to form a gel substance to obtain the modified GO-SiO2Gelling; standing and aging the obtained gel for 10-12 h, and then performing reduced pressure pumping by using a pumping filterFiltering, and washing with deionized water for 5-10 times; drying the mixture in a blast drying oven at 80 ℃ for 5-8 h, and crushing the dried powder to obtain modified GO-SiO2And (4) composite filling.
2. The method according to claim 1, wherein the modifier used in the first step is one or more of p-phenylenediamine, triethylene tetramine, tetraethylene pentamine.
3. The method according to claim 1, wherein the surfactant used in the second step is one or more of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate.
4. The method according to claim 1, wherein the silicon source used in the second step is one or more of tetraethyl orthosilicate, sodium silicate water glass and potassium silicate water glass.
5. Modified GO-SiO2The application of the composite filler in the solution polymerized styrene butadiene rubber is characterized in that the composite filler comprises the following raw materials in parts by mass: 100phr of solution polymerized styrene butadiene rubber SSBR (SLR3402), 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0, 2.5phr of sulfur, 5phr of environment-friendly aromatic oil (TDAE), 0.1phr of antiscorching agent and 0.1phr of modified GO-SiO230 to 50phr of composite filler.
6. A modified GO-SiO according to claim 52The application of the composite filler in the solution polymerized styrene butadiene rubber is characterized by comprising the following steps: the temperature of the torque rheometer is set to be 110 ℃, and the rotating speed of the rotor is 70 r/min; then sequentially adding SSBR, stearic acid, zinc oxide and modified GO-SiO2Carrying out one-stage banburying on the composite filler and the environment-friendly aromatic oil, wherein the banburying time is 7min, the rubber discharging temperature is 140 ℃, and cooling for 4 h; then adding an anti-coking agent, an accelerant CZ, a accelerant DM and sulfur on an open mill with the roll temperature of 60 ℃ for two-stage mixing, adjusting the roll spacing to be 0.8-1.0mm, packaging in a triangular bag, passing through for 7-8 times in a thin mode, adjusting the roll spacing to be 2-3mm, discharging,standing at room temperature for 12-24h, and vulcanizing at 170 deg.C under 12MPa for 10 min.
7. The modified GO-SiO of claim 52The application of the composite filler in the solution polymerized styrene butadiene rubber is characterized in that: modified GO-SiO2The amount of the composite filler was 45 phr.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667186A (en) * | 2021-08-09 | 2021-11-19 | 安徽理工大学 | DDM-GO @ SiO2Composite material, preparation method and application of prepared TPU |
| CN114044939A (en) * | 2021-11-01 | 2022-02-15 | 山东理工大学 | Preparation method of high-dispersion anti-aging nano filler for tire |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854387A (en) * | 2017-01-04 | 2017-06-16 | 华南理工大学 | A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application |
| CN107022119A (en) * | 2017-05-15 | 2017-08-08 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide/rubber composite |
| CN107325328A (en) * | 2017-06-15 | 2017-11-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN108424622A (en) * | 2018-04-25 | 2018-08-21 | 南通海大新材料科技有限公司 | A kind of modified graphene oxide/epoxy resin composite material and its preparation method and application |
| CN108530699A (en) * | 2018-05-15 | 2018-09-14 | 四川大学 | A kind of preparation method of polymer modification graphene composite material |
| CN109867830A (en) * | 2019-01-16 | 2019-06-11 | 中国石油天然气股份有限公司 | Anti-aging nitrile butadiene rubber/o-phenylenediamine modified graphene oxide composite material |
| CN110117390A (en) * | 2019-05-23 | 2019-08-13 | 河北科技大学 | A kind of graphene oxide modified anti-aging agent, thermo oxidative aging rubber and preparation method comprising it |
| CN110283369A (en) * | 2019-05-27 | 2019-09-27 | 江苏大学 | Heat oxygen aging resistance epoxy natural rubber nanocomposite and preparation method thereof |
| CN111690186A (en) * | 2020-06-23 | 2020-09-22 | 扬州华通橡塑有限公司 | High-wear-resistance and impact-resistant composite rubber and preparation method thereof |
| CN111978737A (en) * | 2020-08-17 | 2020-11-24 | 绍兴市卓诚新材料有限公司 | Heat-conducting insulating silicon rubber thermoplastic elastic composite material and preparation method thereof |
-
2021
- 2021-02-21 CN CN202110194737.1A patent/CN112980217B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854387A (en) * | 2017-01-04 | 2017-06-16 | 华南理工大学 | A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application |
| CN107022119A (en) * | 2017-05-15 | 2017-08-08 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide/rubber composite |
| CN107325328A (en) * | 2017-06-15 | 2017-11-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN108424622A (en) * | 2018-04-25 | 2018-08-21 | 南通海大新材料科技有限公司 | A kind of modified graphene oxide/epoxy resin composite material and its preparation method and application |
| CN108530699A (en) * | 2018-05-15 | 2018-09-14 | 四川大学 | A kind of preparation method of polymer modification graphene composite material |
| CN109867830A (en) * | 2019-01-16 | 2019-06-11 | 中国石油天然气股份有限公司 | Anti-aging nitrile butadiene rubber/o-phenylenediamine modified graphene oxide composite material |
| CN110117390A (en) * | 2019-05-23 | 2019-08-13 | 河北科技大学 | A kind of graphene oxide modified anti-aging agent, thermo oxidative aging rubber and preparation method comprising it |
| CN110283369A (en) * | 2019-05-27 | 2019-09-27 | 江苏大学 | Heat oxygen aging resistance epoxy natural rubber nanocomposite and preparation method thereof |
| CN111690186A (en) * | 2020-06-23 | 2020-09-22 | 扬州华通橡塑有限公司 | High-wear-resistance and impact-resistant composite rubber and preparation method thereof |
| CN111978737A (en) * | 2020-08-17 | 2020-11-24 | 绍兴市卓诚新材料有限公司 | Heat-conducting insulating silicon rubber thermoplastic elastic composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667186A (en) * | 2021-08-09 | 2021-11-19 | 安徽理工大学 | DDM-GO @ SiO2Composite material, preparation method and application of prepared TPU |
| CN114044939A (en) * | 2021-11-01 | 2022-02-15 | 山东理工大学 | Preparation method of high-dispersion anti-aging nano filler for tire |
| CN114044939B (en) * | 2021-11-01 | 2023-03-31 | 山东理工大学 | Preparation method of high-dispersion anti-aging nano filler for tire |
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