CN112980217B - Modified GO-SiO 2 Preparation method of composite filler and application of composite filler in rubber - Google Patents
Modified GO-SiO 2 Preparation 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 67
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 63
- 239000000945 filler Substances 0.000 title claims abstract description 60
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000005060 rubber Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 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
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 229920006978 SSBR Polymers 0.000 claims description 20
- 235000019353 potassium silicate Nutrition 0.000 claims description 17
- 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
- 238000003756 stirring Methods 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000010692 aromatic oil 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
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 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
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000004111 Potassium silicate Substances 0.000 claims description 7
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052913 potassium silicate Inorganic materials 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 group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 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
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 239000012763 reinforcing filler Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 description 12
- 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 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000009566 rice Nutrition 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
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- C08K3/34—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
-
- 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
-
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention belongs to the technical field of nano composite materials, in particular to a modified GO-SiO 2 The invention provides a preparation method of a composite filler and application of the composite filler in rubber, and provides a preparation method for constructing modified Graphene Oxide (GO) -silicon dioxide (SiO) 2 ) Is a composite filler for solving the problem of GO and SiO 2 The dispersion effect in rubber is poor, the problem of easy agglomeration is solved, and meanwhile, the anti-aging performance of the composite filler is endowed by modifying GO. Firstly, utilizing an amino modifier to modify GO in one step through a hydrothermal method, wherein the modified GO presents a three-dimensional hole structure; then the silicon source is used for making SiO through an in-situ growth method 2 Particles are deposited and interpenetrated on the surface and holes of the modified GO; to obtain novel modified GO-SiO 2 A composite filler; the method can effectively solve the problem of agglomeration of the reinforcing filler, reduce the interaction between the filler and the filler, and improve the mechanical property and the ageing resistance of the rubber.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a modified GO-SiO 2 A preparation method of composite filler and application thereof in rubber.
Background
Graphene is a carbonaceous material with a monolayer two-dimensional honeycomb lattice structure formed by closely stacking sp2 hybridized connected carbon atoms. Graphene has an infinitely repeated periodic structure in a plane, and has only nano-scale in a direction perpendicular to the plane, and can be regarded as a nano material with macroscopic dimensions. Graphene has high specific surface area, large aspect ratio, high modulus and good solvent dispersibility, and is a potential rubber reinforcing filler. The structure and the performance of GO and graphene are similar, the surface groups are numerous, the cost is low, and the GO and graphene become excellent fillers of polymers such as rubber and plastics, but the GO is easy to be aggregated in a polymer matrix to cause the decrease of the rubber performance.
SiO 2 As 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 SiO 2 The dispersion in rubber is also a major difficulty due to the small particle size, which has a strong tendency to aggregate.
Disclosure of Invention
The invention aims to develop a modified GO-SiO 2 Composite filler, with emphasis on solving GO and SiO 2 The reinforcing filler has the anti-aging effect. The invention mainly uses the modifier to modify GO into a three-dimensional hole structure, thereby increasing the specific surface area; construction of modified GO-SiO by in situ growth 2 Sol to SiO 2 Load and interpenetration in the modified GO pore structure, and the modifier endows GO with anti-aging propertyCan ensure that the rubber can be added into rubber to achieve the reinforcing effect and simultaneously avoid GO and SiO 2 Agglomeration in the rubber matrix.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention provides a modified GO-SiO 2 The preparation method of the composite filler comprises the following steps:
step one: preparing modified GO: firstly, mixing GO and water in a mass ratio of 1: (40-60) mixing to obtain an aqueous solution of GO, and placing the aqueous solution into an ultrasonic cleaner 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 an aqueous solution of GO with the concentration of 16-25 mg/ml; then adding a modifier and ammonia water with 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, a step of selecting a specific type of material; magnetically stirring for 20min at 25-30 ℃, adding the mixture 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-SiO 2 Composite filler: firstly, the modified GO obtained in the first step and deionized water are mixed according to the mass ratio of 1:1200 are mixed to obtain a modified GO aqueous solution, the modified GO aqueous solution is placed in an ultrasonic cleaner for ultrasonic dispersion, the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, the ultrasonic time is 25-35min, and the modified GO aqueous solution with the concentration of 0.83mg/ml is prepared; then mixing a silicon source and the modified GO dispersion liquid according to a mass ratio of 1:5, mixing to obtain a mixed solution, and 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, keeping the constant temperature of the mixed solution at 0-5 ℃, and adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the silicon source to the dilute hydrochloric acid is 1:2.5, dripping and stirring at the same time, wherein the dripping time is 4-6 hours, forming a gel substance, and obtaining the modified GO-SiO 2 Gel; finally, standing and aging the obtained gel for 10-12 hours, then performing vacuum filtration by using a suction filter, and washing with deionized water for 5-10 times; drying in a blowing drying oven at 80 ℃ for 5-8 h, and further crushing the dried powder to obtain modified GO-SiO 2 And (3) a composite filler.
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 hexadecyl 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-SiO 2 The application of the composite filler in the solution polymerized styrene-butadiene rubber SSBR comprises the following raw materials in parts by mass: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 30 to 50phr of composite filler.
Modified GO-SiO 2 The application of the SSBR composite material in the solution polymerized styrene-butadiene rubber SSBR comprises the following steps: the temperature of the torque rheometer is set to 110 ℃, and the rotating speed of the rotor is 70r/min; sequentially adding SSBR, stearic acid, zinc oxide and modified GO-SiO according to the formula 2 Carrying out primary banburying on the composite filler and the environment-friendly aromatic oil for 7min, discharging the rubber at 140 ℃, and cooling for 4h; adding a scorch retarder, promoters CZ, DM and sulfur on an open mill with a roller temperature of 60 ℃ for two-stage mixing, adjusting the roller spacing to 0.8-1.0mm, packing in a triangular bag, carrying out thin ventilation for 7-8 times, adjusting the roller spacing to 2-3mm, placing at room temperature for 12-24h, vulcanizing under the conditions of 170 ℃ multiplied by 12MPa multiplied by 10min, and modifying GO-SiO 2 The composite filler was 45phr.
Compared with the prior art, the invention provides a modified GO-SiO 2 The preparation method of the composite filler and the application of the composite filler in rubber have the following beneficial effects: the modified GO-SiO provided by the invention 2 The preparation method of the composite filler has simple system and process and is easy to expand. Modified GO-SiO 2 The 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 by selecting a GO modifier, so that the nano-composite filler is preparedA three-dimensional nano carbon material with rice size, large specific surface area and porous performance. The composite filler can be used as an excellent material for rubber reinforcement; in addition, anti-aging modification of GO also makes it possible to replace anti-aging agents in rubber.
Drawings
FIG. 1 shows a modified GO-SiO according to the present invention 2 Drawing profile of the stretched cross section of the solution polymerized styrene-butadiene rubber composite when the composite particles were filled with 45phr.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Example 1
Step one: preparing modified GO: firstly, mixing GO and water in a mass ratio of 1:50, placing the mixture into an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30 minutes, so as to obtain the GO aqueous solution with the concentration of 20 mg/ml; then adding modifier Tetraethylenepentamine (TEPA) and ammonia water with pH=10-11 into the GO aqueous solution, wherein the volume ratio of the TEPA to the ammonia water to the GO aqueous solution is 6:2:25, a step of selecting a specific type of material; magnetically stirring at 25deg.C for 20min, adding into a hydrothermal reaction kettle, reacting at 180deg.C for 10 hr, and cooling; washing 5 times with deionized water to remove unreacted TEPA, and freeze drying for 48h gave modified GO.
Step two: preparation of modified GO-SiO 2 Composite filler: firstly, the modified GO obtained in the first step and deionized water are mixed according to the mass ratio of 1:1200, and then obtaining a modified GO aqueous solution, and placing the modified GO aqueous solution in an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30 minutes, so as to obtain a modified GO aqueous solution with the concentration of 0.83 mg/ml; then, the potassium silicate water glass with the modulus of 3.3 and the modified GO dispersion liquid are mixed according to the mass ratio of 1:5, mixing to obtain a mixed solution, and then 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, keeping the temperature of the mixed solution at 0-5 ℃, adding 1mol/L dilute hydrochloric acid and silicic acidThe mass ratio of the potash water glass to the dilute hydrochloric acid is 1:2.5, dripping and stirring at the same time, wherein the dripping time is 5 hours, forming a gelatinous substance, and obtaining the modified GO-SiO 2 Gel; finally, standing and aging the obtained gel for 10 hours, then performing vacuum filtration by using a suction filter, and washing with deionized water for 5 times; drying in a blowing drying oven at 80 ℃ for 5 hours, and further crushing the dried powder to obtain modified GO-SiO 2 And (3) a composite filler.
Modified GO-SiO 2 Application of composite filler in solution polymerized styrene butadiene rubber SSBR, and modified GO-SiO prepared by adopting method 2 The composite filler comprises the following rubber experimental formula in parts by weight: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 30phr of composite filler.
The temperature of the torque rheometer is set to 110 ℃, and the rotating speed of the rotor is 70r/min; sequentially adding SSBR, stearic acid, zinc oxide and modified GO-SiO according to the formula 2 Carrying out primary banburying on the composite filler and the environment-friendly aromatic oil for 7min, discharging the rubber at 140 ℃, and cooling for 4h; adding an anti-coking agent, promoters CZ, DM and sulfur on an open mill at the roller temperature of 60 ℃ for two-stage mixing, adjusting the roller spacing to 0.8-1.0mm, packing in a triangular bag, carrying out thin ventilation for 7-8 times, adjusting the roller spacing to 2-3mm, placing at room temperature for 12-24h, and vulcanizing at 170 ℃ multiplied by 12MPa multiplied by 10 min.
Example 2
Taking the modified GO-SiO prepared in example 1 above 2 The composite filler comprises the following rubber experimental formula in parts by weight: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 35phr of composite.
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Example 3
Taking the modified GO-SiO prepared in example 1 above 2 The compound filler, rubber experimental formula and mass fraction are as follows: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 40phr of composite.
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Example 4
Taking the modified GO-SiO prepared in example 1 above 2 The composite filler comprises the following rubber experimental formula in parts by weight: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 45phr of composite.
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Example 5
Taking the modified GO-SiO prepared in example 1 above 2 The composite filler comprises the following rubber experimental formula in parts by weight: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, modified GO-SiO 2 50phr of composite.
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Comparative example 1
Preparation of GO-SiO 2 Composite filler: (1) mixing GO and deionized water according to a mass ratio of 1:1200 are mixed to obtain GO aqueous solution, and the GO aqueous solution is placed in an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic frequency is 40kHz, the temperature is 25 ℃, and the ultrasonic time is 30min, so that the GO aqueous solution with the concentration of 0.83mg/ml is prepared; (2) Mixing potassium silicate water glass with a modulus of 3.3 with 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, keeping the constant temperature of the mixed solution at 0-5 ℃, and adding 1mol/L dilute hydrochloric acid, wherein the mass ratio of the potassium silicate water glass to the dilute hydrochloric acid is 1:25, dropwise adding and stirring for 5 hours to form a gel substance to obtain GO-SiO 2 Gel; (3) Standing and aging the obtained gel for 10 hours, then performing vacuum filtration by using a suction filter, and washing with deionized water for 5 times; drying in a blowing drying oven at 80deg.C for 5 hr, and pulverizing to obtain GO-SiO 2 And (3) a composite filler.
GO-SiO 2 Application of composite filler in SSBR, and prepared GO-SiO 2 The composite filler comprises the following rubber experimental formula in parts by weight: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, GO-SiO 2 45phr of composite.
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Comparative example 2
Preparation of SiO 2 : (1) Mixing potassium silicate water glass with the modulus of 3.3 with deionized water according to the 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, keeping the constant temperature of the mixed solution at 0-5 ℃, and adding 1mol/L dilute hydrochloric acid, wherein the mass ratio of the potassium silicate water glass to the dilute hydrochloric acid is 1:2.5, dropwise adding and stirring for 5 hours to form a gel substance to obtain SiO 2 Gel; (2) Standing and aging the obtained gel for 10 hours, then performing vacuum filtration by using a suction filter, and washing with deionized water for 5 times; drying in a blowing drying oven at 80 ℃ for 5 hours, and further crushing the dried powder to obtain SiO 2 And (3) filling.
SiO 2 Application in SSBR, taking the prepared SiO 2 The rubber experiment formula and the mass parts are as follows: SSBR (SLR 3402) 100phr, zinc oxide 6phr, stearic acid 1phr, accelerator CZ0.7phr, accelerator DM0.6phr, sulfur 2.5phr, environment-friendly aromatic oil (TDAE) 5phr, scorch retarder 0.1phr, siO 2 45phr。
According to the above formulation, a vulcanized rubber was prepared according to the method for preparing a vulcanized rubber in example 1 and tested for various basic properties.
Comparative examples 1-2 and examples 1-5 were subjected to mechanical property tests, and the test results are shown in Table 1:
TABLE 1 mechanical Properties of rubber composite
As can be seen from Table 1, with the modified GO-SiO 2 The tensile strength, elongation at break and tear strength of the SSBR composites in examples 1-5 increased with increasing filler fraction and then decreased, with increasing Shore A hardness. The improvement of mechanical properties is mainly due to the modification of GO-SiO 2 The composite filler reacts with the rubber matrix to form a better binding force; the decrease is mainly due to the modification of GO-SiO 2 The increase of the filling amount of the composite filler gradually reduces the dispersibility in the rubber, so that stress concentration and interface separation are easy to generate in performance test, and the capability of the rubber for resisting external force is reduced under continuous load. When modifying GO-SiO 2 When the composite reached 45phr, i.e. example 4, the SSBR composite had better overall mechanical properties. As can be seen from the mechanical properties of comparative examples 1-2 and example 4, the modified GO-SiO 2 The mechanical property of the composite reinforced rubber is obviously improved mainly due to the modified GO-SiO 2 The surface grafted hydrophobic groups improve their dispersibility in rubber and compare to SiO 2 And GO-SiO 2 The unique reticular hole structure of the composite material is tightly combined with the rubber matrix, so that the mechanical property of the rubber is improved.
The aging resistance tests of comparative examples 1 to 2 and examples 1 to 5 were conducted, and the test results are shown in Table 2:
TABLE 2 ageing resistance of rubber composites
Note that: negative values indicate a decrease in the value after aging, and positive values indicate an increase.
As can be seen from Table 2, examples 1 to 5 showed that the Shore A hardness, tensile strength and tear strength of the rubber all tended to rise and then fall with increasing filler fraction after the thermo-oxidative aging test (70 ℃ C. Times.72 h), indicating that the modified GO-SiO 2 The addition of the composite filler can improve the ageing resistance of the rubber composite material. Under the condition of thermal oxidation aging, free radicals generated by rubber are captured by primary amine groups and secondary amine groups on the surface of modified GO, and chain termination is initiated, so that an anti-aging effect is achieved; the trend was reduced due to the modified GO-SiO 2 The excessive addition of the composite filler causes agglomeration in rubber, so that the filler is separated from a rubber interface, and the anti-aging effect is reduced; taken together, the best anti-aging effect at example 4, i.e., modified GO-SiO 2 The effect of the composite filler is most excellent when 45phr is filled. Comparative examples 1-2 are inferior in mechanical properties to example 4 after aging experiments compared with example 4, and are mainly SiO 2 And GO-SiO 2 The composite filler has a main reinforcing effect in a rubber matrix, and the modified GO-SiO 2 The composite filler has a reinforcing effect, and meanwhile, the modified GO surface grafted group has an anti-aging effect and can keep good mechanical properties.
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 (4)
1. Modified GO-SiO 2 The preparation method of the composite filler is characterized by comprising the following steps:
step one: preparing modified GO: firstly, mixing GO and water in a mass ratio of 1: (40-60) mixing to obtain an aqueous solution of GO, and placing the aqueous solution into an ultrasonic cleaner 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 an aqueous solution of GO with the concentration of 16-25 mg/ml; then adding a modifier and ammonia water with 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, a step of selecting a specific type of material; magnetically stirring for 20min at 25-30 ℃, adding the mixture 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 48 hours to obtain modified GO; the modifier is tetraethylenepentamine;
step two: preparation of modified GO-SiO 2 Composite filler: firstly, the modified GO obtained in the first step and deionized water are mixed according to the mass ratio of 1:1200 are mixed to obtain a modified GO aqueous solution, the modified GO aqueous solution is placed in an ultrasonic cleaner for ultrasonic dispersion, the ultrasonic frequency is 35-40 kHz, the temperature is 25-30 ℃, the ultrasonic time is 25-35min, and the modified GO aqueous solution with the concentration of 0.83mg/ml is prepared; then mixing a silicon source and the modified GO dispersion liquid according to a mass ratio of 1:5, mixing to obtain a mixed solution, and 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, keeping the constant temperature of the mixed solution at 0-5 ℃, and adding 1mol/L of dilute hydrochloric acid, wherein the mass ratio of the silicon source to the dilute hydrochloric acid is 1:2.5, dripping and stirring at the same time, wherein the dripping time is 4-6 hours, forming a gel substance, and obtaining the modified GO-SiO 2 Gel; standing and aging the obtained gel for 10-12 hours, then performing vacuum filtration by using a suction filter, and washing with deionized water for 5-10 times; drying in a blowing drying oven at 80 ℃ for 5-8 h, and crushing the dried powder to obtain modified GO-SiO 2 A composite filler;
the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and sodium dodecyl sulfonate;
the silicon source is one or more of tetraethyl orthosilicate, sodium silicate water glass and potassium silicate water glass.
2. A modified GO-SiO prepared by the method of claim 1 2 The application of the composite filler in solution polymerized styrene-butadiene rubber is characterized in thatThe raw materials comprise the following components in parts by mass: 100phr of solution polymerized styrene-butadiene rubber SSBR, 6phr of zinc oxide, 1phr of stearic acid, 0.7phr of accelerator CZ, 0.6phr of accelerator DM0.6phr of sulfur, 2.5phr of environment-friendly aromatic oil, 0.1phr of scorch retarder and modified GO-SiO 2 30 to 50phr of composite filler.
3. The modified GO-SiO according to claim 2 2 The application of the composite filler in solution polymerized styrene-butadiene rubber is characterized by comprising the following steps: the temperature of the torque rheometer is set to 110 ℃, and the rotating speed of the rotor is 70r/min; sequentially adding SSBR, stearic acid, zinc oxide and modified GO-SiO 2 Carrying out primary banburying on the composite filler and the environment-friendly aromatic oil for 7min, discharging the rubber at 140 ℃, and cooling for 4h; adding an anti-coking agent, promoters CZ, DM and sulfur on an open mill at the roller temperature of 60 ℃ for two-stage mixing, adjusting the roller spacing to 0.8-1.0mm, packing in a triangular bag, carrying out thin ventilation for 7-8 times, adjusting the roller spacing to 2-3mm, placing at room temperature for 12-24h, and vulcanizing at 170 ℃ multiplied by 12MPa multiplied by 10 min.
4. The modified GO-SiO according to claim 2 2 The application of the composite filler in solution polymerized styrene-butadiene rubber is characterized in that: modified GO-SiO 2 The composite filler was 45phr.
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