CN106633422A - Graphene modified rubber material - Google Patents
Graphene modified rubber material Download PDFInfo
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- CN106633422A CN106633422A CN201610905966.9A CN201610905966A CN106633422A CN 106633422 A CN106633422 A CN 106633422A CN 201610905966 A CN201610905966 A CN 201610905966A CN 106633422 A CN106633422 A CN 106633422A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a graphene modified rubber material, which includes the following raw materials: ethylene propylene rubber, ethylene propylene diene monomer, graphene, dibutyl ester, furfuryl alcohol resin, glycerol triglyceride, stearyl acrylate, a maleic anhydride grafted compound, magnesium hydroxide, kaolin, talcum powder, cetyl calcium sulfonate, diethyl zinc dithiocarbamate, chlorinated polyethylene, isoprene, microcrystalline wax, lignocellulose, dimethyl silicone oil, carbon fibers, polyamide fibers, carboxyethyl cellulose, a surfactant, an initiator, a chain extender, a crosslinker, a degassing agent, a flatting agent, a catalyst, an accelerant, a plasticizer, a dispersing agent, a tackifier, a curing agent, an antibacterial agent, an antioxidant, a light stabilizer, a thermal stabilizer, an anti-aging agent, an ultraviolet absorber, a flame retarder and a smoke inhibitor. The material has good flame-retarding effect, is strong in anti-impact capability and toughness, and can be widely applied for production of tyres, rubber hoses, rubber belts, cables, etc. The material has significant economic and social benefit.
Description
Technical field
The invention belongs to elastomeric material preparing technical field, and in particular to a kind of Graphene modified rubber material.
Background technology
Rubber（Rubber）：Strong flexible polymer material with reversible deformation.High resilience at room temperature, in very little
External force effect is lower to be produced compared with large deformation, remove resilient after external force.Rubber belongs to entirely without styling polymer, its glass
Glass transition temperature（Tg）Low, molecular weight is often very big, more than hundreds of thousands.
The word of rubber one derives from Indian cau-uchu, means " tree for shedding tears ".Natural rubber is exactly by Hevea rubber
The latex flowed out during tree rubber tapping is obtained Jing solidification, after being dried.1770, Britain chemist J. Priestleys had found that rubber can
For wiping pencil writing, at that time the material of this purposes was referred to as into rubber, this word is used till today always.The strand of rubber
Can be crosslinked, when the rubber after crosslinking is deformed by external force effect, with the rapid ability restored, and with good physics
Mechanical property and chemical stability.Rubber is the base stock of rubber industry, is widely used in manufacture tire, sebific duct, adhesive tape, cable
And other various rubbers.Rubber is divided into natural rubber and synthetic rubber by raw material.By form be divided into block rubber, latex,
Liquid rubber and powdered rubber.Latex is the colloidal aqueous dispersion of rubber；Liquid rubber for rubber oligomer, it is unvulcanized before
Generally sticky liquid；Powdered rubber is that latex is processed into powdered, with sharp dispensing and processing and fabricating.The sixties in 20th century
The thermoplastic elastomer of exploitation, without the need for chemical cure, and adopts the processing method of thermoplastic to shape.Rubber is by using being divided into again
The universal and class of Special type two.Insulator, it is not easy to conductive, but if get wet or different temperature if, it is possible to become
Conductor.Conduction is the easy situation of conduction of the electronics with regard to material interior molecules or ion.
The Geim and Novoselov of Man Chesidun universities of Britain in 2004 peels off high starch breeding and obtains solely by adhesive tape
The vertical two-dimensional graphene for existing（Gra-phene, GN）Since crystal, it is extremely concerned that Graphene has become material science
One of study hotspot.The graphite of Graphene, actually monoatomic layer, it possesses the two-dimensional structure and excellent power of uniqueness
, thermodynamics, optically and electrically performance.
Graphene be it is at present most thin in the world be but also most hard nano material, it is almost fully transparent, to inhaling
2.3% light is received, thermal conductivity factor is up to 5300W/mk, higher than CNT and diamond.Graphene is one kind by carbon atom structure
Into individual layer laminated structure new material, high with intensity, specific surface area is big, high chemical reactivity, the characteristics of high fillibility.
Existing rubber there are problems that anti-flammability and other, how Graphene to be filled to enter into rubber
Row is modified, so as to obtain rubber of good performance, becomes a kind of research tendency.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Graphene modified rubber material, existing rubber flame-retarded to solve
The problems such as property and other poor mechanical properties.The Graphene modified rubber material good flame retardation effect of the present invention, strong shock resistance is tough
Property it is strong, be a kind of excellent Graphene modified rubber material of performance, can be widely applied to manufacture tire, sebific duct, adhesive tape, cable and its
His various rubbers, with significant economic and social benefit.
In order to solve above technical problem, the present invention is employed the following technical solutions：
A kind of Graphene modified rubber material, in units of weight portion, including following raw material：EP rubbers 76-104 parts, ternary
EP rubbers 48-62 parts, Graphene 43-64 parts, dibutyl ester 22-35 parts, furfuryl alcohol resin 18-22 parts, glycerine glycerinate
16-26 parts, stearyl acrylate acid esters 12-15 parts, maleic anhydride grafting 16-23 parts, magnesium hydroxide 4-6 parts, kaolin 7-10 parts,
Talcum powder 5-9 parts, cetyl sulfoacid calcium 4-8 part, zinc diethyl dithiocarbamate 5-12 parts, haloflex 12-16
Part, isoprene 12-16 parts, microwax 14-23 parts, lignocellulosic 9-15 parts, dimethicone 8-13 parts, carbon fiber 7-12
Part, Fypro 4-6 parts, carboxyethyl cellulose 5-9 parts, surfactant 0.6-1.2 parts, initiator 0.4-0.6 parts, chain extension
Agent 0.6-0.8 parts, crosslinking agent 0.3-0.5 parts, degasser 0.3-0.4 parts, levelling agent 0.4-0.7 parts, catalyst 0.2-0.4 parts,
Accelerator 0.2-0.3 parts, plasticizer 0.3-0.5 parts, dispersant 0.2-0.4 parts, tackifier 0.3-0.4 parts, curing agent 0.7-1.1
Part, antiseptic 0.6-1.2 parts, antioxidant 0.4-0.6 parts, light stabilizer 0.2-0.4 parts, heat stabilizer 0.1-0.2 parts, antiager
0.6-1.2 parts, ultra-violet absorber 0.4-0.6 parts, fire retardant 1.2-1.5 parts, smoke suppressant 0.5-0.8 part；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 parts, without phenyl ring oxygen tree
Fat 20-34 parts, AESA 18-25 parts, tripentaerythritol 12-22 parts, urea 10-16 parts, aluminum oxide
7-12 parts, antimony oxide 9-12 parts, manganese oxide 5-9 parts, atlapulgite 8-12 parts, bleeding agent 1.3-1.8 parts, synergist 0.8-
1.2 part；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 22-43 parts, molybdenum hydroxide 12-20
Part, bentonite 10-16 parts, aluminum oxide 6-12 parts, ammonium octamolybdate 4-7 parts, stearic acid 1.2-2 parts；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, 300-500 mesh sieve is crossed, powder is obtained, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and temperature is 42-53 DEG C, and rotating speed is under 200-300r/min, to stir 22-36min, and graphite is obtained
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 63-74 DEG C in temperature, rotating speed is
0.9-1.4h is activated under 120-150r/min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 186-257W in microwave power, and temperature is 128-
134 DEG C, rotating speed is to stir 2-4h under 300-500r/min, and mixture I is obtained；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 66-72 DEG C in temperature, and rotating speed is to stir 1.2-1.6 under 100-200r/min
H, is obtained mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 parts are added in microwave reactor, is 400- in speed of agitator
6-10min is stirred under 600r/min, mixture A is obtained；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature is obtained mixture B to stir 2-2.5h at 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained fire retardant to water content≤3.4%；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
200-400r/min, microwave power is 200-250W, and temperature is obtained mixture C to stir 1.3-1.8h at 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained smoke suppressant to water content≤2.8%；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melting extrusion under conditions of 600r/min, is granulated by tank tie rod and in pelleter, and Graphene modified rubber material is obtained
Material.
Further, the surfactant is surfactant TRITONCF-10.
Further, the initiator is dibenzoyl peroxide.
Further, the chain extender is methyl diphenylene diisocyanate.
Further, the crosslinking agent is Methacrylamide.
Further, the degasser is stearic acid.
Further, the levelling agent is polyether polyester azo polyether polyeste.
Further, the catalyst is three（Dimethylamino-propyl）Hexahydrotriazine.
Further, the accelerator is colourless cobalt.
Further, the plasticizer is citrate.
The invention has the advantages that：
（1）The Graphene modified rubber material of the present invention has high flame resistance and smoke suppressing effect, and will not discharge has at high temperature
Malicious harmful substance, it is to avoid the secondary injury to human body；
（2）The Graphene modified rubber material good flame retardation effect of the present invention, strong shock resistance, toughness is strong, is that a kind of performance is excellent
Graphene modified rubber material, preparation cost is low, can be applicable, and has significant economic and social benefit.
（3）The present invention Graphene modified rubber material can be widely applied to manufacture tire, sebific duct, adhesive tape, cable and its
His various rubbers, good flame retardation effect, it is impossible to burning and form flame, it is stable and reliable for performance.
Specific embodiment
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to the present invention's
Protection domain, but do not limit the scope of the invention.
In embodiment, the Graphene modified rubber material, in units of weight portion, including following raw material：The rubber of second third
Glue 76-104 parts, ethylene propylene diene rubber 48-62 parts, Graphene 43-64 parts, dibutyl ester 22-35 parts, furfuryl alcohol resin 18-22 parts, third
Triol glycerinate 16-26 part, stearyl acrylate acid esters 12-15 parts, maleic anhydride grafting 16-23 parts, magnesium hydroxide 4-6
Part, kaolin 7-10 parts, talcum powder 5-9 parts, cetyl sulfoacid calcium 4-8 part, zinc diethyl dithiocarbamate 5-12 parts,
Haloflex 12-16 parts, isoprene 12-16 parts, microwax 14-23 parts, lignocellulosic 9-15 parts, dimethicone 8-
13 parts, carbon fiber 7-12 parts, Fypro 4-6 parts, carboxyethyl cellulose 5-9 parts, surfactant 0.6-1.2 parts, cause
Agent 0.4-0.6 parts, chain extender 0.6-0.8 parts, crosslinking agent 0.3-0.5 parts, degasser 0.3-0.4 parts, levelling agent 0.4-0.7 parts,
Catalyst 0.2-0.4 parts, accelerator 0.2-0.3 parts, plasticizer 0.3-0.5 parts, dispersant 0.2-0.4 parts, tackifier 0.3-0.4
Part, curing agent 0.7-1.1 parts, antiseptic 0.6-1.2 parts, antioxidant 0.4-0.6 parts, light stabilizer 0.2-0.4 parts, heat stabilizer
0.1-0.2 parts, antiager 0.6-1.2 parts, ultra-violet absorber 0.4-0.6 parts, fire retardant 1.2-1.5 parts, smoke suppressant 0.5-0.8
Part；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The crosslinking agent is Methacrylamide；
The degasser is stearic acid；
The levelling agent is polyether polyester azo polyether polyeste；
The catalyst is three（Dimethylamino-propyl）Hexahydrotriazine；
The accelerator is colourless cobalt；
The plasticizer is citrate；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 parts, without phenyl ring oxygen tree
Fat 20-34 parts, AESA 18-25 parts, tripentaerythritol 12-22 parts, urea 10-16 parts, aluminum oxide
7-12 parts, antimony oxide 9-12 parts, manganese oxide 5-9 parts, atlapulgite 8-12 parts, bleeding agent 1.3-1.8 parts, synergist 0.8-
1.2 part；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 22-43 parts, molybdenum hydroxide 12-20
Part, bentonite 10-16 parts, aluminum oxide 6-12 parts, ammonium octamolybdate 4-7 parts, stearic acid 1.2-2 parts；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, 300-500 mesh sieve is crossed, powder is obtained, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and temperature is 42-53 DEG C, and rotating speed is under 200-300r/min, to stir 22-36min, and graphite is obtained
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 63-74 DEG C in temperature, rotating speed is
0.9-1.4h is activated under 120-150r/min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 186-257W in microwave power, and temperature is 128-
134 DEG C, rotating speed is to stir 2-4h under 300-500r/min, and mixture I is obtained；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 66-72 DEG C in temperature, and rotating speed is to stir 1.2-1.6 under 100-200r/min
H, is obtained mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 parts are added in microwave reactor, is 400- in speed of agitator
6-10min is stirred under 600r/min, mixture A is obtained；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature is obtained mixture B to stir 2-2.5h at 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained fire retardant to water content≤3.4%；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
200-400r/min, microwave power is 200-250W, and temperature is obtained mixture C to stir 1.3-1.8h at 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained smoke suppressant to water content≤2.8%；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melting extrusion under conditions of 600r/min, is granulated by tank tie rod and in pelleter, and Graphene modified rubber material is obtained
Material.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of Graphene modified rubber material, in units of weight portion, including following raw material：EP rubbers 76-104 parts, ternary
55 parts of EP rubbers, 52 parts of Graphene, 30 parts of dibutyl ester, 20 parts of furfuryl alcohol resin, 22 parts of glycerine glycerinate, acrylic acid are hard
14 parts of resin acid ester, 20 parts of maleic anhydride grafting, 5 parts of magnesium hydroxide, 8 parts of kaolin, 7 parts of talcum powder, cetyl sulfoacid calcium 6
Part, 8 parts of zinc diethyl dithiocarbamate, 14 parts of haloflex, 14 parts of isoprene, 18 parts of microwax, wood fibre
12 parts of element, 12 parts of dimethicone, 10 parts of carbon fiber, 5 parts of Fypro, 7 parts of carboxyethyl cellulose, surfactant 0.9
Part, 0.5 part of initiator, 0.7 part of chain extender, 0.4 part of crosslinking agent, 0.3 part of degasser, 0.6 part of levelling agent, 0.3 part of catalyst, rush
Enter 0.2 part of agent, 0.4 part of plasticizer, 0.3 part of dispersant, 0.3 part of tackifier, 0.9 part of curing agent, 0.8 part of antiseptic, antioxidant
0.5 part, 0.3 part of light stabilizer, 0.1 part of heat stabilizer, 0.9 part of antiager, 0.5 part of ultra-violet absorber, 1.4 parts of fire retardant,
0.7 part of smoke suppressant；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The crosslinking agent is Methacrylamide；
The degasser is stearic acid；
The levelling agent is polyether polyester azo polyether polyeste；
The catalyst is three（Dimethylamino-propyl）Hexahydrotriazine；
The accelerator is colourless cobalt；
The plasticizer is citrate；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：56 parts of ethylene glycol ether acetate, without benzene epoxy resin 26
Part, 22 parts of AESA, 18 parts of tripentaerythritol, 14 parts of urea, 10 parts of aluminum oxide, antimony oxide 10
Part, 7 parts of manganese oxide, 10 parts of atlapulgite, 1.6 parts of bleeding agent, 1 part of synergist；
The smoke suppressant is in units of weight portion, including following raw material：32 parts of tributyltin oxide, 16 parts of molybdenum hydroxide, swelling
14 parts of soil, 8 parts of aluminum oxide, 6 parts of ammonium octamolybdate, 1.6 parts of stearic acid；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, cross 400 mesh sieve, be obtained powder, gained powder magnetic field intensity be 6000GS, ultrasonic wave work(
Rate is 420W, and temperature is 46 DEG C, and rotating speed is under 260r/min, to stir 30min, and Graphene energy powder is obtained；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 67 DEG C in temperature, rotating speed is 140r/
1.2h is activated under min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 230W in microwave power, and temperature is 132 DEG C, is turned
Speed is obtained mixture I to stir 3h under 400r/min；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 70 DEG C in temperature, and rotating speed is to stir 1.5 h under 150r/min, and mixing is obtained
Thing II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, 280 parts of water are added in microwave reactor, is 500r/min in speed of agitator
Lower stirring 8min, is obtained mixture A；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, speed of agitator be 400r/min, microwave
Power is 240W, and temperature is obtained mixture B to stir 2.3h at 90 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 4000r/min
It is 3.4% to be dried to water content, and fire retardant is obtained；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
300r/min, microwave power is 220W, and temperature is obtained mixture C to stir 1.5h at 112 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 4000r/min
It is 2.8% to be dried to water content, and smoke suppressant is obtained；
S5：Add in double screw extruder to mixture II obtained in step S4, be 232 DEG C in temperature, rotating speed is 500r/min
Under conditions of melting extrusion, granulate by tank tie rod and in pelleter, Graphene modified rubber material is obtained.
Embodiment 2
A kind of Graphene modified rubber material, in units of weight portion, including following raw material：76 parts of EP rubbers, EPDM
48 parts of rubber, 43 parts of Graphene, 22 parts of dibutyl ester, 18 parts of furfuryl alcohol resin, 16 parts of glycerine glycerinate, stearyl acrylate acid
12 parts of ester, maleic anhydride be grafted 16 parts, 4 parts of magnesium hydroxide, 7 parts of kaolin, 5 parts of talcum powder, 4 parts of cetyl sulfoacid calcium, two
5 parts of zinc diethyl dithiocarbamate, 12 parts of haloflex, 12 parts of isoprene, 14 parts of microwax, 9 parts of lignocellulosic,
8 parts of dimethicone, 7 parts of carbon fiber, 4 parts of Fypro, 5 parts of carboxyethyl cellulose, 0.6 part of surfactant, initiator
0.4 part, 0.6 part of chain extender, 0.3 part of crosslinking agent, 0.3 part of degasser, 0.4 part of levelling agent, 0.2 part of catalyst, accelerator 0.2
Part, 0.3 part of plasticizer, 0.2 part of dispersant, 0.3 part of tackifier, 0.7 part of curing agent, 0.6 part of antiseptic, 0.4 part of antioxidant, light
0.2 part of stabilizer, 0.1 part of heat stabilizer, 0.6 part of antiager, 0.4 part of ultra-violet absorber, 1.2 parts of fire retardant, smoke suppressant 0.5
Part；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The crosslinking agent is Methacrylamide；
The degasser is stearic acid；
The levelling agent is polyether polyester azo polyether polyeste；
The catalyst is three（Dimethylamino-propyl）Hexahydrotriazine；
The accelerator is colourless cobalt；
The plasticizer is citrate；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：48 parts of ethylene glycol ether acetate, without benzene epoxy resin 20
Part, 18 parts of AESA, 12 parts of tripentaerythritol, 10 parts of urea, 7 parts of aluminum oxide, antimony oxide 9
Part, 5 parts of manganese oxide, 8 parts of atlapulgite, 1.3 parts of bleeding agent, 0.8 part of synergist；
The smoke suppressant is in units of weight portion, including following raw material：22 parts of tributyltin oxide, 12 parts of molybdenum hydroxide, swelling
10 parts of soil, 6 parts of aluminum oxide, 4 parts of ammonium octamolybdate, 1.2 parts of stearic acid；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, cross 300 mesh sieve, be obtained powder, gained powder magnetic field intensity be 5830GS, ultrasonic wave work(
Rate is 350W, and temperature is 42 DEG C, and rotating speed is under 200r/min, to stir 36min, and Graphene energy powder is obtained；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 63 DEG C in temperature, rotating speed is 120r/
1.4h is activated under min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 186W in microwave power, and temperature is 128 DEG C, is turned
Speed is obtained mixture I to stir 4h under 300r/min；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 66 DEG C in temperature, and rotating speed is to stir 1.6 h under 100r/min, and mixing is obtained
Thing II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, 240 parts of water are added in microwave reactor, is 400r/min in speed of agitator
Lower stirring 10min, is obtained mixture A；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, speed of agitator be 300r/min, microwave
Power is 220W, and temperature is obtained mixture B to stir 2.5h at 86 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 3000r/min
It is 3.2% to be dried to water content, and fire retardant is obtained；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
200r/min, microwave power is 200W, and temperature is obtained mixture C to stir 1.8h at 106 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 3000r/min
It is 2.3% to be dried to water content, and smoke suppressant is obtained；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224 DEG C in temperature, rotating speed is 400r/min
Under conditions of melting extrusion, granulate by tank tie rod and in pelleter, Graphene modified rubber material is obtained.
Embodiment 3
A kind of Graphene modified rubber material, in units of weight portion, including following raw material：104 parts of EP rubbers, EPDM
62 parts of rubber, 64 parts of Graphene, 35 parts of dibutyl ester, 22 parts of furfuryl alcohol resin, 26 parts of glycerine glycerinate, stearyl acrylate acid
15 parts of ester, maleic anhydride be grafted 23 parts, 6 parts of magnesium hydroxide, 10 parts of kaolin, 9 parts of talcum powder, 8 parts of cetyl sulfoacid calcium, two
12 parts of zinc diethyl dithiocarbamate, 16 parts of haloflex, 16 parts of isoprene, 23 parts of microwax, lignocellulosic 15
Part, 13 parts of dimethicone, 12 parts of carbon fiber, 6 parts of Fypro, 9 parts of carboxyethyl cellulose, 1.2 parts of surfactant, draw
Send out 0.6 part of agent, 0.8 part of chain extender, 0.5 part of crosslinking agent, 0.4 part of degasser, 0.7 part of levelling agent, 0.4 part of catalyst, accelerator
0.3 part, 0.5 part of plasticizer, 0.4 part of dispersant, 0.4 part of tackifier, 1.1 parts of curing agent, 1.2 parts of antiseptic, antioxidant 0.6
Part, 0.4 part of light stabilizer, 0.2 part of heat stabilizer, 1.2 parts of antiager, 0.6 part of ultra-violet absorber, 1.5 parts of fire retardant, suppression cigarette
0.8 part of agent；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The crosslinking agent is Methacrylamide；
The degasser is stearic acid；
The levelling agent is polyether polyester azo polyether polyeste；
The catalyst is three（Dimethylamino-propyl）Hexahydrotriazine；
The accelerator is colourless cobalt；
The plasticizer is citrate；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：65 parts of ethylene glycol ether acetate, without benzene epoxy resin 34
Part, 25 parts of AESA, 22 parts of tripentaerythritol, 16 parts of urea, 12 parts of aluminum oxide, antimony oxide 12
Part, 9 parts of manganese oxide, 12 parts of atlapulgite, 1.8 parts of bleeding agent, 1.2 parts of synergist；
The smoke suppressant is in units of weight portion, including following raw material：43 parts of tributyltin oxide, 20 parts of molybdenum hydroxide, swelling
16 parts of soil, 12 parts of aluminum oxide, 7 parts of ammonium octamolybdate, 2 parts of stearic acid；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, cross 500 mesh sieve, be obtained powder, gained powder magnetic field intensity be 6250GS, ultrasonic wave work(
Rate is 480W, and temperature is 53 DEG C, and rotating speed is under 300r/min, to stir 22min, and Graphene energy powder is obtained；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 74 DEG C in temperature, rotating speed is 150r/
0.9h is activated under min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 257W in microwave power, and temperature is 134 DEG C, is turned
Speed is obtained mixture I to stir 2h under 500r/min；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 72 DEG C in temperature, and rotating speed is to stir 1.2 h under 200r/min, and mixing is obtained
Thing II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, 300 parts of water are added in microwave reactor, is 600r/min in speed of agitator
Lower stirring 6min, is obtained mixture A；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, speed of agitator be 500r/min, microwave
Power is 250W, and temperature is obtained mixture B to stir 2h at 93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 5000r/min
It is 3.2% to be dried to water content, and fire retardant is obtained；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
400r/min, microwave power is 250W, and temperature is obtained mixture C to stir 1.3h at 118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, be centrifuged in the case where rotating speed is 5000r/min
It is 2.2% to be dried to water content, and smoke suppressant is obtained；
S5：Add in double screw extruder to mixture II obtained in step S4, be 235 DEG C in temperature, rotating speed is 600r/min
Under conditions of melting extrusion, granulate by tank tie rod and in pelleter, Graphene modified rubber material is obtained.
After testing, its performance is as shown in the table for Graphene modified rubber material prepared by the present embodiment 1-3：
As seen from the above table, Graphene modified rubber material good flame retardation effect of the invention, strong shock resistance, toughness is strong, is one
The excellent Graphene modified rubber material of performance is planted, can be applicable, there is significant economic and social benefit.
Above content it cannot be assumed that the present invention be embodied as be confined to these explanation, for belonging to the present invention technology neck
For the those of ordinary skill in domain, without departing from the inventive concept of the premise, some simple deduction or replace can also be made,
The scope of patent protection that the present invention is determined by the claims submitted to should be all considered as belonging to.
Claims (10)
1. a kind of Graphene modified rubber material, it is characterised in that in units of weight portion, including following raw material：EP rubbers
76-104 parts, ethylene propylene diene rubber 48-62 parts, Graphene 43-64 parts, dibutyl ester 22-35 parts, furfuryl alcohol resin 18-22 parts, the third three
Alcohol glycerinate 16-26 part, stearyl acrylate acid esters 12-15 parts, maleic anhydride grafting 16-23 parts, magnesium hydroxide 4-6 parts,
Kaolin 7-10 parts, talcum powder 5-9 parts, cetyl sulfoacid calcium 4-8 part, zinc diethyl dithiocarbamate 5-12 parts, chlorine
Change polyethylene 12-16 parts, isoprene 12-16 parts, microwax 14-23 parts, lignocellulosic 9-15 parts, dimethicone 8-13
Part, carbon fiber 7-12 parts, Fypro 4-6 parts, carboxyethyl cellulose 5-9 parts, surfactant 0.6-1.2 parts, initiator
0.4-0.6 parts, chain extender 0.6-0.8 parts, crosslinking agent 0.3-0.5 parts, degasser 0.3-0.4 parts, levelling agent 0.4-0.7 parts, urge
Agent 0.2-0.4 part, accelerator 0.2-0.3 parts, plasticizer 0.3-0.5 parts, dispersant 0.2-0.4 parts, tackifier 0.3-0.4
Part, curing agent 0.7-1.1 parts, antiseptic 0.6-1.2 parts, antioxidant 0.4-0.6 parts, light stabilizer 0.2-0.4 parts, heat stabilizer
0.1-0.2 parts, antiager 0.6-1.2 parts, ultra-violet absorber 0.4-0.6 parts, fire retardant 1.2-1.5 parts, smoke suppressant 0.5-0.8
Part；
The dispersant is dispersant NC；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antiseptic is lithium carbonate；
The antioxidant is antioxidant 1010；
The light stabilizer is light stabilizer 770；
The heat stabilizer is Dythal；
The antiager is BASF UV-234 antiagers;
The ultra-violet absorber is septichen phenyl ester；
The fire retardant is in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 parts, without phenyl ring oxygen tree
Fat 20-34 parts, AESA 18-25 parts, tripentaerythritol 12-22 parts, urea 10-16 parts, aluminum oxide
7-12 parts, antimony oxide 9-12 parts, manganese oxide 5-9 parts, atlapulgite 8-12 parts, bleeding agent 1.3-1.8 parts, synergist 0.8-
1.2 part；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 22-43 parts, molybdenum hydroxide 12-20
Part, bentonite 10-16 parts, aluminum oxide 6-12 parts, ammonium octamolybdate 4-7 parts, stearic acid 1.2-2 parts；
The preparation method of the Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, 300-500 mesh sieve is crossed, powder is obtained, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and temperature is 42-53 DEG C, and rotating speed is under 200-300r/min, to stir 22-36min, and graphite is obtained
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, is 63-74 DEG C in temperature, rotating speed is
0.9-1.4h is activated under 120-150r/min, activation Graphene energy powder is obtained；
S3：Under nitrogen protection, EP rubbers, ethylene-propylene-diene monomer are added in activation Graphene energy powder obtained in step S2
Glue, dibutyl ester, furfuryl alcohol resin, glycerine glycerinate, stearyl acrylate acid esters, maleic anhydride grafting, magnesium hydroxide, kaolinite
Soil, talcum powder, cetyl sulfoacid calcium, zinc diethyl dithiocarbamate, haloflex, isoprene, microwax, wood
Matter cellulose, dimethicone, carbon fiber, Fypro, carboxyethyl cellulose, initiator, chain extender, crosslinking agent, degassing
Agent, levelling agent, catalyst, accelerator, plasticizer, dispersant, tackifier, are 186-257W in microwave power, and temperature is 128-
134 DEG C, rotating speed is to stir 2-4h under 300-500r/min, and mixture I is obtained；
S4：Curing agent, antiseptic, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, ultra-violet absorber, fire retardant, smoke suppressant, are 66-72 DEG C in temperature, and rotating speed is to stir 1.2-1.6 under 100-200r/min
H, is obtained mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 parts are added in microwave reactor, is 400- in speed of agitator
6-10min is stirred under 600r/min, mixture A is obtained；
（b）To in mixture A obtained in step a add ethylene glycol ether acetate, without benzene epoxy resin, tripentaerythritol, urine
Element, aluminum oxide, antimony oxide, manganese oxide, atlapulgite, bleeding agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature is obtained mixture B to stir 2-2.5h at 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained fire retardant to water content≤3.4%；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, bentonite, aluminum oxide, ammonium octamolybdate, stearic acid mixing, it is in speed of agitator
200-400r/min, microwave power is 200-250W, and temperature is obtained mixture C to stir 1.3-1.8h at 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 3000-5000r/min
Centrifugal drying is obtained smoke suppressant to water content≤2.8%；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melting extrusion under conditions of 600r/min, is granulated by tank tie rod and in pelleter, and Graphene modified rubber material is obtained
Material.
2. Graphene modified rubber material according to claim 1, it is characterised in that the surfactant is that surface is lived
Property agent TRITONCF-10.
3. Graphene modified rubber material according to claim 1, it is characterised in that the initiator is diphenyl peroxide
Formyl.
4. Graphene modified rubber material according to claim 1, it is characterised in that the chain extender is diphenyl methane
Diisocyanate.
5. Graphene modified rubber material according to claim 1, it is characterised in that the crosslinking agent is methacryl
Amine.
6. Graphene modified rubber material according to claim 1, it is characterised in that the degasser is stearic acid.
7. Graphene modified rubber material according to claim 1, it is characterised in that the levelling agent changes for polyether polyester
Property organosiloxane.
8. Graphene modified rubber material according to claim 1, it is characterised in that the catalyst is three（Diformazan ammonia
Base propyl group）Hexahydrotriazine.
9. Graphene modified rubber material according to claim 1, it is characterised in that the accelerator is colourless cobalt.
10. Graphene modified rubber material according to claim 1, it is characterised in that the plasticizer is citrate.
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541154A (en) * | 2017-09-30 | 2018-01-05 | 江苏瑞和新材料股份有限公司 | Modified chlorinated natural rubber adhesive of graphene and preparation method thereof |
| CN108424584A (en) * | 2018-03-12 | 2018-08-21 | 厦门力嘉诚防水工程有限公司 | A kind of graphene EPDM root-resistance waterproof coiled material |
| CN109688751A (en) * | 2019-01-10 | 2019-04-26 | 国网新疆电力有限公司吐鲁番供电公司 | A kind of intelligent control switch system convenient for assembling |
| CN109762221A (en) * | 2019-01-15 | 2019-05-17 | 安徽大学 | A kind of graphene oxide-loaded galapectite modified styrene butadiene rubber and preparation method thereof |
| CN111791543A (en) * | 2020-06-22 | 2020-10-20 | 中裕软管科技股份有限公司 | High-heat-conductivity rubber hose and manufacturing method thereof |
| CN114927268A (en) * | 2022-04-11 | 2022-08-19 | 浙江元通线缆制造有限公司 | Photoelectric composite cable for coal mining machine |
| CN115651321A (en) * | 2022-09-30 | 2023-01-31 | 威海市泓淋电力技术股份有限公司 | High-insulation boiling-resistant ethylene propylene diene monomer rubber mixture and preparation method thereof |
| CN117286609A (en) * | 2023-11-27 | 2023-12-26 | 吴江京奕特种纤维有限公司 | Bio-based yarn and vortex spinning preparation method thereof |
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| CN1439671A (en) * | 2002-08-01 | 2003-09-03 | 阜新橡胶有限责任公司 | Smokeless flame resistant conveying belt without halide |
| CN105111531A (en) * | 2015-04-29 | 2015-12-02 | 宁波职业技术学院 | Graphene-modified wear-resistant rubber |
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| CN1439671A (en) * | 2002-08-01 | 2003-09-03 | 阜新橡胶有限责任公司 | Smokeless flame resistant conveying belt without halide |
| CN105111531A (en) * | 2015-04-29 | 2015-12-02 | 宁波职业技术学院 | Graphene-modified wear-resistant rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541154A (en) * | 2017-09-30 | 2018-01-05 | 江苏瑞和新材料股份有限公司 | Modified chlorinated natural rubber adhesive of graphene and preparation method thereof |
| CN107541154B (en) * | 2017-09-30 | 2019-07-19 | 江苏瑞和新材料股份有限公司 | Modified chlorinated natural rubber adhesive of graphene and preparation method thereof |
| CN108424584A (en) * | 2018-03-12 | 2018-08-21 | 厦门力嘉诚防水工程有限公司 | A kind of graphene EPDM root-resistance waterproof coiled material |
| CN109688751A (en) * | 2019-01-10 | 2019-04-26 | 国网新疆电力有限公司吐鲁番供电公司 | A kind of intelligent control switch system convenient for assembling |
| CN109762221A (en) * | 2019-01-15 | 2019-05-17 | 安徽大学 | A kind of graphene oxide-loaded galapectite modified styrene butadiene rubber and preparation method thereof |
| CN111791543A (en) * | 2020-06-22 | 2020-10-20 | 中裕软管科技股份有限公司 | High-heat-conductivity rubber hose and manufacturing method thereof |
| CN114927268A (en) * | 2022-04-11 | 2022-08-19 | 浙江元通线缆制造有限公司 | Photoelectric composite cable for coal mining machine |
| CN114927268B (en) * | 2022-04-11 | 2023-09-08 | 浙江元通线缆制造有限公司 | Photoelectric composite cable for coal mining machine |
| CN115651321A (en) * | 2022-09-30 | 2023-01-31 | 威海市泓淋电力技术股份有限公司 | High-insulation boiling-resistant ethylene propylene diene monomer rubber mixture and preparation method thereof |
| CN117286609A (en) * | 2023-11-27 | 2023-12-26 | 吴江京奕特种纤维有限公司 | Bio-based yarn and vortex spinning preparation method thereof |
| CN117286609B (en) * | 2023-11-27 | 2024-01-30 | 吴江京奕特种纤维有限公司 | Bio-based yarn and vortex spinning preparation method thereof |
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Application publication date: 20170510 |