CN109957158A - Modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method - Google Patents
Modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method Download PDFInfo
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- CN109957158A CN109957158A CN201711399077.0A CN201711399077A CN109957158A CN 109957158 A CN109957158 A CN 109957158A CN 201711399077 A CN201711399077 A CN 201711399077A CN 109957158 A CN109957158 A CN 109957158A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
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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
- C08K3/18—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
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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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- Polymers & Plastics (AREA)
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Abstract
The present invention relates to a kind of containing graphene/white carbon black styrene-butadiene rubber composite materials of modification, are the rubber composite materials prepared using emulsion blending co-agglomeration.Each raw material in the present invention: graphene, phyllosilicate, white carbon black, mass ratio are 1~5:1~10:1~70, and liquid modifying agent accounts for the 0.1~5% of rubber dry glue quality, and dispersing agent accounts for the 0.01~0.5% of filler siccative quality.Slurries are added in the styrene-butadiene latex solution for being 100 parts containing liquid modifying agent dry rubber content by 1~70 part of filler, after high-speed stirred, washing solid through acid cure, drying obtain modified rubber composite material；Modified graphene/white carbon black/styrene-butadiene rubber composite material prepared by the present invention, with lower Mooney viscosity and heat, higher modulus, tear resistance and the good wear-resisting property of lower rolling resistance, the invention is simple and feasible, it is at low cost, be easy to industrialize, have preferable economic benefit and social benefit.
Description
Technical field
This application involves modified styrene butadiene rubber technical field of composite materials, more particularly relate to a kind of graphene/white carbon black/
The preparation method of styrene-butadiene rubber composite material.
Background technique
Graphene is a kind of hexagonal lattice flat film being made of carbon atom with sp2 hybridized orbit, only one or
The two-dimensional material of multiple carbon atom thickness.Graphene has excellent mechanical, thermally conductive, electric conductivity, is current most attractive
One of inorganic nano material, be current two-dimentional carbon nanomaterial newest, research is most hot, performance is best.Graphene is used for
Tire preparation, applied to the tyre surface of tire, base rubber, sidewall, tire shoulder, triangle rubber, belt compound, carcass glue, transition zone glue, gas
Close layer glue etc. can effectively solve phenomena such as existing tire quality difference is easily blown out.Graphene chemical stability is high, with other media
Interaction it is weaker, but due to the single layer structure of graphene, so that the specific surface area with superelevation, to easily crimp
And reunion (atomic interaction between a piece of becomes curling, and interaction generates reunion between piece and piece), this allows for stone
Black alkene is difficult to be uniformly dispersed when being filled other substances, significantly limits graphene and further answers in rubber materials
With.Therefore, it is necessary to which graphene and other fillers to be used in combination, graphene rubber composite material is prepared.
Carry out filled rubber using the graphene oxide part substitution white carbon black of height removing, the rubber nano being prepared
In composite material, since graphene and white carbon black intert mutually effective aggregation for inhibiting two kinds of fillers itself, so that they
Disperse more uniform, shows do not losing the original excellent properties of white carbon black (higher modulus, lower rolling resistance)
While, the wear-resisting property of rubber material is significantly improved, and further increase the modulus and tear resistance of composite material
Energy.Since white carbon black is three-dimensional globular nanofiller, partial size is about tens nanometers, and graphene oxide is two-dimensional sheet filler,
Major diameter is bigger, therefore using difference a combination of the two of the two in dimension and size to generate synergistic effect；While by
In generating apparent hydrogen bond action between the two, to realize the complementation and nanometer reinforcement effect of white carbon black and graphene oxide
Fruit further improves the mechanical mechanics property of vulcanized rubber.Simultaneously because the lamellar structure of graphene oxide and good
Automatic recovery ability also imparts the good gas barrier property of rubber material and self-healing capability, has conventional filler incomparable
Advantage.With graphene and white carbon black and be used to enhance or be modified preparation rubber nano composite material have it is more excellent comprehensive
Performance is closed, can be widely applied to the industrial products such as tire, offset plate, adhesive tape, rubber roller, conveyer belt and various field of sealing technology, Yi Jihang
Empty space industry.
Summary of the invention
The purpose of the present invention is to propose to a kind of preparations of modified styrene butadiene rubber composite material containing graphene and white carbon black
Method comprising rubber matrix and add auxiliary agent accordingly.With high abrasion, strong mechanical performance, high-specific surface area, (limiting value is reachable
2630m2/ g) graphene and the good white carbon black of cheap phyllosilicate, tear resistance, Heveatex be raw material,
Composite material is prepared into using wet process, improves dispersibility of the filler in rubber matrix, assigns the good processing of butadiene-styrene rubber
Performance, high abrasion, high tear performance etc..
A kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method, which is characterized in that including following
Step: being separately added into graphene, phyllosilicate, white carbon black in the reactor, and mass ratio is 0.1~5:1~10:1~70,
Water, dispersing agent carry out high-speed stirred, are prepared into and disperse uniform slurries；Slurries are added to containing liquid by 1~70 part of filler
It in modifying agent, the styrene-butadiene latex solution that dry rubber content is 100 parts, mixes under high velocity agitation, washing solid through acid cure, drying obtain
To modified graphene/white carbon black/styrene-butadiene rubber composite material；The graphene is single-layer graphene or multi-layer graphene or changes
Property graphene or modified graphene oxide.
The phyllosilicate be talcum, pyrophillite, mica, kaolinite, vermiculite, montmorillonite, serpentine, sepiolite,
One of palygorskite.
Modifying agent in the slurries is Heveatex, epoxy natural latex, carboxylic chloroprene rubber latex or NBR latex etc.
Any one or mixture, account for the 0.1~5% of rubber dry glue quality.
Dispersing agent in the slurries be neopelex, polyvinyl alcohol, lauryl sodium sulfate it is any one
Kind or mixture, account for the 0.01~0.5% of filler siccative quality.
The invention has the benefit that modified graphene/white carbon black/styrene-butadiene rubber composite material, is blended using wet process
Prepared by mode, improve dispersibility and uniformity of the filler in butadiene-styrene rubber；Graphene because of itself unique performance so that
Composite material has high-wearing feature and strong mechanical performance；Phyllosilicate, price is lower, compensate for graphene price it is high lack
Point；White carbon black improves the tear resistance of sizing material.
Specific embodiment
The present invention is proposed by preparing graphene/white carbon black and styrene-butadiene latex suspension, using emulsion blending co-coagulation work
Skill prepares modified graphene/white carbon black/styrene-butadiene rubber composite material, to improve dispersion of the white carbon black in rubber matrix, is
The performance for improving white carbon black modified rubber composite material opens up new approach.In graphene/white carbon black slurries preparation process
It is stirred using high shear force, is prepared for stable graphene/white carbon black slurries, the modification of graphene and white carbon black surface enhances
The compatibility of white carbon black and styrene-butadiene latex, so that graphene/white carbon black obtains good dispersity, rubber in styrene-butadiene latex
Performance be improved.Prepared white carbon black modified styrene-butadiene composite material is not only used directly for after vulcanizing agent is added
Processing rubber product, and can be widely applied for the fields such as composite modification.
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually
According to normal conditions.
Embodiment 1
1 part of graphene, 4 parts of kaolin, 30 parts of white carbon black are sequentially added in the reactor, and quality is than 100 parts of water, dispersing agent 12
Sodium alkyl benzene sulfonate 0.1g, high-speed stirred 30min are prepared into and disperse uniform slurries；It takes 100 parts of mixed slurry to be added to be mixed with
5 parts of Heveatex, styrene-butadiene latex 100 parts (solid content 25%) mixed emulsion in, mix under high velocity agitation, it is solid through acid cure, wash
It washs, dry, obtain modified graphene/white carbon black/styrene-butadiene rubber composite material；100 parts of composite materials are taken, 50 parts of carbon black, are aoxidized
5 parts of zinc, 3 parts of stearic acid, 2 parts of sulphur, 1 part of accelerator NS is kneaded on a mill；Vulcanized on vulcanizing press, sulphur
Change 150 DEG C of temperature.The physical mechanical property of its raw rubber is shown in Table 1.
Embodiment 2
2 parts of graphene, 4 parts of kaolin, 30 parts of white carbon black are sequentially added in the reactor, and quality is than 100 parts of water, dispersing agent 12
Sodium alkyl benzene sulfonate 0.1g, high-speed stirred 30min are prepared into and disperse uniform slurries；It takes 100 parts of mixed slurry to be added to be mixed with
5 parts of Heveatex, styrene-butadiene latex 100 parts (solid content 25%) mixed emulsion in, mix under high velocity agitation, it is solid through acid cure, wash
It washs, dry, obtain modified graphene/white carbon black/styrene-butadiene rubber composite material；100 parts of composite materials are taken, 50 parts of carbon black, are aoxidized
It 5 parts of zinc, 3 parts of stearic acid, 2 parts of sulphur, 1 part of accelerator NS, is kneaded on a mill；Vulcanized on vulcanizing press, sulphur
Change 150 DEG C of temperature.The physical mechanical property of its raw rubber is shown in Table 1.
Embodiment 3
3 parts of graphene, 4 parts of kaolin, 30 parts of white carbon black are sequentially added in the reactor, and quality is than 100 parts of water, dispersing agent 12
Sodium alkyl benzene sulfonate 0.1g, high-speed stirred 30min are prepared into and disperse uniform slurries；It takes 100 parts of mixed slurry to be added to be mixed with
5 parts of Heveatex, styrene-butadiene latex 100 parts (solid content 25%) mixed emulsion in, mix under high velocity agitation, it is solid through acid cure, wash
It washs, dry, obtain modified graphene/white carbon black/styrene-butadiene rubber composite material；100 parts of composite materials are taken, 50 parts of carbon black, are aoxidized
5 parts of zinc, 3 parts of stearic acid, 2 parts of sulphur, 1 part of accelerator NS is kneaded on a mill；Vulcanized on vulcanizing press, sulphur
Change 150 DEG C of temperature.The physical mechanical property of its raw rubber is shown in Table 1.
Comparative example 1
1 part of graphene is sequentially added in the reactor, and 30 parts of white carbon black, quality is than 100 parts of water, dispersing agent dodecyl benzene sulfonic acid
Sodium 0.1g, high-speed stirred 30min are prepared into and disperse uniform slurries；It takes 100 parts of mixed slurry to be added to and is mixed with Heveatex 5
Part, in the mixed emulsion of styrene-butadiene latex 100 parts (solid content 25%), mix under high velocity agitation, it is, washing solid through acid cure, dry,
Obtain modified graphene/white carbon black/styrene-butadiene rubber composite material；Take 100 parts of composite materials, 50 parts of carbon black, 5 parts of zinc oxide, firmly
3 parts of resin acid, 2 parts of sulphur, 1 part of accelerator NS is kneaded on a mill；Vulcanized on vulcanizing press, curing temperature 150
℃.The physical mechanical property of its raw rubber is shown in Table 1.
The performance of 1 embodiment of the present invention of table and comparative example compares
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Mooney viscosity | 73 | 72 | 70 | 76 |
| Hardness/Shao Er A | 65 | 60 | 62 | 70 |
| Tensile strength/MPa | 23.5 | 25.6 | 27.3 | 22.1 |
| Tearing strength/KN/m | 120 | 126 | 130 | 110 |
Claims (5)
1. a kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method, which is characterized in that including following step
It is rapid: it is separately added into graphene, phyllosilicate, white carbon black in the reactor, mass ratio is 0.1~5:1~10:1~70, water,
Dispersing agent carries out high-speed stirred, is prepared into and disperses uniform slurries；Slurries are added to by 1~70 part of filler and are changed containing liquid
Property agent, dry rubber content be to be mixed under high velocity agitation in 100 parts of styrene-butadiene latex solution, it is, washing solid through acid cure, dry, obtain
Modified graphene/white carbon black/styrene-butadiene rubber composite material.
2. a kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method according to claim 1,
Be characterized in that: the graphene is single-layer graphene or multi-layer graphene or modified graphene or modified graphene oxide.
3. a kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method according to claim 1,
Be characterized in that: layered silicate is talcum, pyrophillite, mica, kaolinite, vermiculite, montmorillonite, serpentine, sepiolite, slope
One of thread stone.
4. a kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method according to claim 1,
Be characterized in that: the modifying agent in the slurries is Heveatex, epoxy natural latex, carboxylic chloroprene rubber latex or NBR latex etc.
Any one or mixture, account for the 0.1~5% of rubber dry glue quality.
5. a kind of modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method according to claim 1,
Be characterized in that: dispersing agent in the slurries be neopelex, polyvinyl alcohol, lauryl sodium sulfate it is any one
Kind or mixture, account for the 0.01~0.5% of filler siccative quality.
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| CN201711399077.0A CN109957158A (en) | 2017-12-22 | 2017-12-22 | Modified graphene/white carbon black/styrene-butadiene rubber composite material preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
| CN113462042A (en) * | 2021-07-26 | 2021-10-01 | 桂林电子科技大学 | Amino modified sepiolite/graphene oxide/natural rubber composite latex and preparation method thereof |
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Patent Citations (6)
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| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| US20130203917A1 (en) * | 2012-02-02 | 2013-08-08 | Lion Copolymer, Llc | Polymer silica-reinforced masterbatch with nanomaterial |
| KR20130048740A (en) * | 2013-04-02 | 2013-05-10 | 이재환 | Liquid curable composition |
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| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
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Application publication date: 20190702 |