CN106433083A - Graphene modified rubber material with high bending strength - Google Patents
Graphene modified rubber material with high bending strength Download PDFInfo
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- CN106433083A CN106433083A CN201610905819.1A CN201610905819A CN106433083A CN 106433083 A CN106433083 A CN 106433083A CN 201610905819 A CN201610905819 A CN 201610905819A CN 106433083 A CN106433083 A CN 106433083A
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
- C08L71/03—Polyepihalohydrins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/02—Flame or fire retardant/resistant
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- 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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Abstract
The invention discloses a graphene modified rubber material with high bending strength. The material is prepared from the following raw materials: epichlorohydrin rubber, neoprene rubber, graphene, tributoxyethyl phosphate, dibutyl phthalate, tris(2,4-ditert-butylphenyl)phosphite, stearyl acrylate, maleic anhydride grafted polymer, magnesium hydroxide, kaolin, carbon black, calcium hexadecanesulfonate, zinc diethyldithiocarbamate, chlorinated polyethylene, isoprene, amide wax, polybutylene terephthalate fiber, dimethicone, carbon fiber, polyamide fiber, carboxyethyl cellulose, surfactant, initiator, chain extender, crosslinking agent, degassing agent, leveling agent, catalyst, promoting agent, plasticizer, dispersant, tackifier, curing agent, antibacterial agent, antioxidant, light stabilizer, heat stabilizer, anti-aging agent, ultraviolet absorber, flame retardant and smoke suppressant. The material has good flame retardancy and high impact resistance and toughness, can be widely used in manufacture of tires, hoses, tapes, cables and other products, and has significant economic and social benefits.
Description
Technical field
The invention belongs to elastomeric material preparing technical field, and in particular to a kind of high bending strength Graphene modified rubber material
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.
One word of rubber derives from Indian cau-uchu, means " tree for shedding tears ".Natural rubber be exactly by Hevea rubber
The latex for flowing out during tree rubber tapping is obtained through solidification, after drying.1770, Britain chemist J. Priestley had found that rubber can
It is used for pencil writing is wiped, at that time the material of this purposes was referred to as 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 that restores, 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, unvulcanized before
Generally sticky liquid；Powdered rubber be latex is processed 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
Universal and two class of Special type.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 university of Britain in 2004 peels off high starch breeding by adhesive tape and obtains solely
The vertical two-dimensional graphene for existing（Gra-phene, GN）Since crystal, it is extremely concerned that Graphene has become as material science
One of study hotspot.The graphite of Graphene, actually monoatomic layer, it has the two-dimensional structure of uniqueness and excellent power
, thermodynamics, optically and electrically performance.
Graphene be 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, heat conductivity is up to 5300W/m k, higher than CNT and diamond.Graphene is one kind by carbon atom structure
The new material of the monolayer laminated structure for becoming, with intensity height, specific surface area is big, high chemical reactivity, the feature of high fillibility.
Existing rubber there are problems of anti-flammability and other, enter in how filling Graphene to rubber
Row is modified, so as to obtain rubber of good performance, becomes a kind of research tendency.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of high bending strength Graphene modified rubber material, existing to solve
The problems such as having rubber flame-retarded property and other poor mechanical property.The fire-retardant effect of the high bending strength Graphene modified rubber material of the present invention
Really good, strong shock resistance, toughness is strong, is a kind of excellent high bending strength Graphene modified rubber material of performance, extensively can answer
For manufacturing tire, sebific duct, adhesive tape, cable and other 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 high bending strength Graphene modified rubber material, in units of weight portion, including following raw material：Chlorohydrin rubber 79-
101 parts, neoprene 50-60 part, Graphene 43-62 part, tributoxyethyl phosphate 24-33 part, dibutyl phthalate
16-24 part, three（2,4- di-tert-butyl-phenyls）Phosphite ester 15-23 part, stearyl acrylate acid esters 12-15 part, maleic anhydride connect
Branch 16-23 part, magnesium hydroxide 4-6 part, Kaolin 7-10 part, white carbon black 5-9 part, cetyl sulfoacid calcium 4-8 part, two sulfur of diethyl
For carbaminate 5-12 part, chlorinated polyethylene 12-16 part, isoprene 12-16 part, amide waxe 14-23 part, poly- terephthaldehyde
Sour butanediol ester fiber 9-15 part, dimethicone 8-13 part, carbon fiber 7-12 part, Fypro 4-6 part, carboxyethylcellulose
Plain 5-9 part, surfactant 0.6-1.2 part, initiator 0.4-0.6 part, chain extender 0.6-0.8 part, cross-linking agent 0.3-0.5 part,
Degasser 0.3-0.4 part, levelling agent 0.4-0.7 part, catalyst 0.2-0.4 part, accelerator 0.2-0.3 part, plasticizer 0.3-0.5
Part, dispersant 0.2-0.4 part, viscosifier 0.3-0.4 part, firming agent 0.7-1.1 part, antibacterial 0.6-1.2 part, antioxidant 0.4-
0.6 part, light stabilizer 0.2-0.4 part, heat stabilizer 0.1-0.2 part, antiager 0.6-1.2 part, UV absorbent 0.4-0.6
Part, fire retardant 1.2-1.5 part, smoke suppressant 0.5-0.8 part；
The dispersant is dispersant NC；
The viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 part, no phenyl ring oxygen tree
Fat 20-34 part, AESA 18-25 part, tripentaerythritol 12-22 part, carbamide 10-16 part, aluminium oxide
7-12 part, antimony oxide 9-12 part, manganese oxide 5-9 part, active hargil 8-12 part, penetrating agent 1.3-1.8 part, synergist 0.8-
1.2 part；
The smoke suppressant in units of weight portion, including following raw material：Tributyltin oxide 22-43 part, molybdenum hydroxide 12-20
Part, Kaolin 10-16 part, aluminium oxide 6-12 part, ammonium octamolybdate 4-7 part, stearic acid 1.2-2 part；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 300-500 mesh sieve, prepared powder, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and it is under 200-300r/min that temperature is 42-53 DEG C, rotating speed, stirs 22-36min, prepared graphite
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, be 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 216-252W in microwave power, and it is to stir 3.4- under 300-500r/min that temperature is 127-133 DEG C, rotating speed
4.5h, prepared mixture I；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, fire retardant, smoke suppressant, are 69-78 DEG C in temperature, and rotating speed is to stir 1-1.4 under 100-200r/min
H, prepared mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 part are added in microwave reactor, is 400- in speed of agitator
6-10min, prepared mixture A is stirred under 600r/min；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature stirs 2-2.5h, prepared mixture B at being 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.4%, prepared fire retardant；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
200-400r/min, microwave power is to stir 1.3-1.8h, prepared mixture C at 200-250W, temperature is 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤2.8%, prepared smoke suppressant；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melt extrude under conditions of 600r/min, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene changes
Property elastomeric material.
Further, the surfactant is surfactant TRITONCF-10.
Further, the initiator is dibenzoyl peroxide.
Further, the chain extender is methyl diphenylene diisocyanate.
Further, the cross-linking 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 high bending strength Graphene modified rubber material of the present invention has high flame resistance and smoke suppressing effect, at high temperature
Poisonous and harmful substance will not be discharged, it is to avoid the secondary injury to human body；
（2）The high bending strength Graphene modified rubber material good flame retardation effect of the present invention, strong shock resistance, toughness is strong, is
A kind of excellent high bending strength Graphene modified rubber material of performance, preparation cost is low, can be applicable, have significant economical and
Social benefit.
（3）The high bending strength Graphene modified rubber material of the present invention can be widely applied to manufacture tire, sebific duct, glue
Band, cable and other various rubbers, good flame retardation effect, it is impossible to burning and formation flame, 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 an embodiment, the high bending strength Graphene modified rubber material, in units of weight portion, including following original
Material：Chlorohydrin rubber 79-101 part, neoprene 50-60 part, Graphene 43-62 part, tributoxyethyl phosphate 24-33 part, neighbour
Phthalic acid dibutyl ester 16-24 part, three（2,4- di-tert-butyl-phenyls）Phosphite ester 15-23 part, stearyl acrylate acid esters 12-15
Part, maleic anhydride grafting 16-23 part, magnesium hydroxide 4-6 part, Kaolin 7-10 part, white carbon black 5-9 part, cetyl sulfoacid calcium 4-8
Part, (DDC)2Zn 5-12 part, chlorinated polyethylene 12-16 part, isoprene 12-16 part, amide waxe 14-23
Part, polybutylene terephthalate (PBT) fiber 9-15 part, dimethicone 8-13 part, carbon fiber 7-12 part, Fypro 4-6
Part, carboxyethyl cellulose 5-9 part, surfactant 0.6-1.2 part, initiator 0.4-0.6 part, chain extender 0.6-0.8 part, crosslinking
Agent 0.3-0.5 part, degasser 0.3-0.4 part, levelling agent 0.4-0.7 part, catalyst 0.2-0.4 part, accelerator 0.2-0.3 part,
Plasticizer 0.3-0.5 part, dispersant 0.2-0.4 part, viscosifier 0.3-0.4 part, firming agent 0.7-1.1 part, antibacterial 0.6-1.2
Part, antioxidant 0.4-0.6 part, light stabilizer 0.2-0.4 part, heat stabilizer 0.1-0.2 part, antiager 0.6-1.2 part, ultraviolet
Absorbent 0.4-0.6 part, fire retardant 1.2-1.5 part, 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 cross-linking 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 viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 part, no phenyl ring oxygen tree
Fat 20-34 part, AESA 18-25 part, tripentaerythritol 12-22 part, carbamide 10-16 part, aluminium oxide
7-12 part, antimony oxide 9-12 part, manganese oxide 5-9 part, active hargil 8-12 part, penetrating agent 1.3-1.8 part, synergist 0.8-
1.2 part；
The smoke suppressant in units of weight portion, including following raw material：Tributyltin oxide 22-43 part, molybdenum hydroxide 12-20
Part, Kaolin 10-16 part, aluminium oxide 6-12 part, ammonium octamolybdate 4-7 part, stearic acid 1.2-2 part；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 300-500 mesh sieve, prepared powder, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and it is under 200-300r/min that temperature is 42-53 DEG C, rotating speed, stirs 22-36min, prepared graphite
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, be 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 216-252W in microwave power, and it is to stir 3.4- under 300-500r/min that temperature is 127-133 DEG C, rotating speed
4.5h, prepared mixture I；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, fire retardant, smoke suppressant, are 69-78 DEG C in temperature, and rotating speed is to stir 1-1.4 under 100-200r/min
H, prepared mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 part are added in microwave reactor, is 400- in speed of agitator
6-10min, prepared mixture A is stirred under 600r/min；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature stirs 2-2.5h, prepared mixture B at being 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.4%, prepared fire retardant；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
200-400r/min, microwave power is to stir 1.3-1.8h, prepared mixture C at 200-250W, temperature is 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤2.8%, prepared smoke suppressant；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melt extrude under conditions of 600r/min, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene changes
Property elastomeric material.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of high bending strength Graphene modified rubber material, in units of weight portion, including following raw material：Chlorohydrin rubber 76-
104 parts, 55 parts of neoprene, 52 parts of Graphene, 30 parts of tributoxyethyl phosphate, 20 parts of dibutyl phthalate, three（2,
4- di-tert-butyl-phenyl）22 parts of phosphite ester, 14 parts of stearyl acrylate acid esters, maleic anhydride be grafted 20 parts, 5 parts of magnesium hydroxide,
8 parts of Kaolin, 7 parts of white carbon black, 6 parts of cetyl sulfoacid calcium, 8 parts of (DDC)2Zn, 14 parts of chlorinated polyethylene,
14 parts of isoprene, 18 parts of amide waxe, 12 parts of polybutylene terephthalate (PBT) fiber, 12 parts of dimethicone, carbon fiber 10
Part, 5 parts of Fypro, 7 parts of carboxyethyl cellulose, 0.9 part of surfactant, 0.5 part of initiator, 0.7 part of chain extender, crosslinking
0.4 part of agent, 0.3 part of degasser, 0.6 part of levelling agent, 0.3 part of catalyst, 0.2 part of accelerator, 0.4 part of plasticizer, dispersant 0.3
Part, 0.3 part of viscosifier, 0.9 part of firming agent, 0.8 part of antibacterial, 0.5 part of antioxidant, 0.3 part of light stabilizer, heat stabilizer 0.1
Part, 0.9 part of antiager, 0.5 part of UV absorbent, 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 cross-linking 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 viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：56 parts of ethylene glycol ether acetate, no benzene epoxy resin 26
Part, 22 parts of AESA, 18 parts of tripentaerythritol, 14 parts of carbamide, 10 parts of aluminium oxide, antimony oxide 10
Part, 7 parts of manganese oxide, 10 parts of active hargil, 1.6 parts of penetrating agent, 1 part of synergist；
The smoke suppressant in units of weight portion, including following raw material：32 parts of tributyltin oxide, 16 parts of molybdenum hydroxide, kaolinite
14 parts of soil, 8 parts of aluminium oxide, 6 parts of ammonium octamolybdate, 1.6 parts of stearic acid；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 400 mesh sieve, prepared powder, gained powder is 6000GS in magnetic field intensity, ultrasound wave work(
Rate is 420W, and it is under 260r/min that temperature is 46 DEG C, rotating speed, stirs 30min, prepared Graphene energy powder；
S2：Surfactant being added in Graphene energy powder obtained in step S1, being 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 230W in microwave power, and it is to stir 3h, prepared mixture I under 400r/min that temperature is 132 DEG C, rotating speed；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, 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, prepared mixture A；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 400r/min in speed of agitator, microwave
Power is 240W, and temperature stirs 2.3h, prepared mixture B at being 90 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 4000r/min
It is 3.4%, prepared fire retardant to dry to water content；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
300r/min, microwave power is to stir 1.5h, prepared mixture C at 220W, temperature is 112 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 4000r/min
It is 2.8%, prepared smoke suppressant to dry to water content；
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 melt extrude, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene modified rubber material
Material.
Embodiment 2
A kind of high bending strength Graphene modified rubber material, in units of weight portion, including following raw material：Chlorohydrin rubber 79
Part, 50 parts of neoprene, 43 parts of Graphene, 24 parts of tributoxyethyl phosphate, 16 parts of dibutyl phthalate, three（2,4-
Di-tert-butyl-phenyl）15 parts of phosphite ester, 12 parts of stearyl acrylate acid esters, 16 parts of maleic anhydride grafting, 4 parts of magnesium hydroxide, height
7 parts of ridge soil, 5 parts of white carbon black, 4 parts of cetyl sulfoacid calcium, 5 parts of (DDC)2Zn, 12 parts of chlorinated polyethylene, different
12 parts of pentadiene, 14 parts of amide waxe, 9 parts of polybutylene terephthalate (PBT) fiber, 8 parts of dimethicone, 7 parts of carbon fiber, poly-
4 parts of nylon, 5 parts of carboxyethyl cellulose, 0.6 part of surfactant, 0.4 part of initiator, 0.6 part of chain extender, cross-linking agent 0.3
Part, 0.3 part of degasser, 0.4 part of levelling agent, 0.2 part of catalyst, 0.2 part of accelerator, 0.3 part of plasticizer, 0.2 part of dispersant, increasing
0.3 part of stick, 0.7 part of firming agent, 0.6 part of antibacterial, 0.4 part of antioxidant, 0.2 part of light stabilizer, 0.1 part of heat stabilizer, anti-
0.6 part of old agent, 0.4 part of UV absorbent, 1.2 parts of fire retardant, 0.5 part of smoke suppressant；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The cross-linking 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 viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：48 parts of ethylene glycol ether acetate, no benzene epoxy resin 20
Part, 18 parts of AESA, 12 parts of tripentaerythritol, 10 parts of carbamide, 7 parts of aluminium oxide, antimony oxide 9
Part, 5 parts of manganese oxide, 8 parts of active hargil, 1.3 parts of penetrating agent, 0.8 part of synergist；
The smoke suppressant in units of weight portion, including following raw material：22 parts of tributyltin oxide, 12 parts of molybdenum hydroxide, kaolinite
10 parts of soil, 6 parts of aluminium oxide, 4 parts of ammonium octamolybdate, 1.2 parts of stearic acid；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 300 mesh sieve, prepared powder, gained powder is 5830GS in magnetic field intensity, ultrasound wave work(
Rate is 350W, and it is under 200r/min that temperature is 42 DEG C, rotating speed, stirs 36min, prepared Graphene energy powder；
S2：Surfactant being added in Graphene energy powder obtained in step S1, being 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 216W in microwave power, and it is to stir 4.5h, prepared mixture I under 300r/min that temperature is 127 DEG C, rotating speed；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, fire retardant, smoke suppressant, are 69 DEG C in temperature, and rotating speed is to stir 1.4 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, prepared mixture A；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 300r/min in speed of agitator, microwave
Power is 220W, and temperature stirs 2.5h, prepared mixture B at being 86 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 3000r/min
It is 3.2%, prepared fire retardant to dry to water content；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
200r/min, microwave power is to stir 1.8h, prepared mixture C at 200W, temperature is 106 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 3000r/min
It is 2.3%, prepared smoke suppressant to dry to water content；
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 melt extrude, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene modified rubber material
Material.
Embodiment 3
A kind of high bending strength Graphene modified rubber material, in units of weight portion, including following raw material：Chlorohydrin rubber 101
Part, 60 parts of neoprene, 62 parts of Graphene, 33 parts of tributoxyethyl phosphate, 24 parts of dibutyl phthalate, three（2,4-
Di-tert-butyl-phenyl）23 parts of phosphite ester, 15 parts of stearyl acrylate acid esters, 23 parts of maleic anhydride grafting, 6 parts of magnesium hydroxide, height
Ridge soil 10 parts, 9 parts of white carbon black, 8 parts of cetyl sulfoacid calcium, 12 parts of (DDC)2Zn, 16 parts of chlorinated polyethylene,
16 parts of isoprene, 23 parts of amide waxe, 15 parts of polybutylene terephthalate (PBT) fiber, 13 parts of dimethicone, carbon fiber 12
Part, 6 parts of Fypro, 9 parts of carboxyethyl cellulose, 1.2 parts of surfactant, 0.6 part of initiator, 0.8 part of chain extender, crosslinking
0.5 part of agent, 0.4 part of degasser, 0.7 part of levelling agent, 0.4 part of catalyst, 0.3 part of accelerator, 0.5 part of plasticizer, dispersant 0.4
Part, 0.4 part of viscosifier, 1.1 parts of firming agent, 1.2 parts of antibacterial, 0.6 part of antioxidant, 0.4 part of light stabilizer, heat stabilizer 0.2
Part, 1.2 parts of antiager, 0.6 part of UV absorbent, 1.5 parts of fire retardant, 0.8 part of smoke suppressant；
The surfactant is surfactant TRITONCF-10；
The initiator is dibenzoyl peroxide；
The chain extender is methyl diphenylene diisocyanate；
The cross-linking 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 viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：65 parts of ethylene glycol ether acetate, no benzene epoxy resin 34
Part, 25 parts of AESA, 22 parts of tripentaerythritol, 16 parts of carbamide, 12 parts of aluminium oxide, antimony oxide 12
Part, 9 parts of manganese oxide, 12 parts of active hargil, 1.8 parts of penetrating agent, 1.2 parts of synergist；
The smoke suppressant in units of weight portion, including following raw material：43 parts of tributyltin oxide, 20 parts of molybdenum hydroxide, kaolinite
16 parts of soil, 12 parts of aluminium oxide, 7 parts of ammonium octamolybdate, 2 parts of stearic acid；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 500 mesh sieve, prepared powder, gained powder is 6250GS in magnetic field intensity, ultrasound wave work(
Rate is 480W, and it is under 300r/min that temperature is 53 DEG C, rotating speed, stirs 22min, prepared Graphene energy powder；
S2：Surfactant being added in Graphene energy powder obtained in step S1, being 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 252W in microwave power, and it is to stir 3.4h, prepared mixture I under 500r/min that temperature is 133 DEG C, rotating speed；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, fire retardant, smoke suppressant, are 78 DEG C in temperature, and rotating speed is to stir 1 h, prepared mixture under 200r/min
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, prepared mixture A；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 500r/min in speed of agitator, microwave
Power is 250W, and temperature stirs 2h, prepared mixture B at being 93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 5000r/min
It is 3.2%, prepared fire retardant to dry to water content；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
400r/min, microwave power is to stir 1.3h, prepared mixture C at 250W, temperature is 118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 5000r/min
It is 2.2%, prepared smoke suppressant to dry to water content；
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 melt extrude, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene modified rubber material
Material.
After testing, its performance is as shown in the table for high bending strength Graphene modified rubber material prepared by the present embodiment 1-3：
As seen from the above table, the high bending strength Graphene modified rubber material good flame retardation effect of the present invention, strong shock resistance, tough
Property strong, be a kind of excellent high bending strength Graphene modified rubber material of performance, can be applicable have significant economical and social
Benefit.
Above content it cannot be assumed that the present invention be embodied as be confined to these explanations, for the present invention affiliated 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 should be all considered as belonging to by the claims that is submitted to.
Claims (10)
1. a kind of high bending strength Graphene modified rubber material, it is characterised in that in units of weight portion, including following original
Material：Chlorohydrin rubber 79-101 part, neoprene 50-60 part, Graphene 43-62 part, tributoxyethyl phosphate 24-33 part, neighbour
Phthalic acid dibutyl ester 16-24 part, three（2,4- di-tert-butyl-phenyls）Phosphite ester 15-23 part, stearyl acrylate acid esters 12-15
Part, maleic anhydride grafting 16-23 part, magnesium hydroxide 4-6 part, Kaolin 7-10 part, white carbon black 5-9 part, cetyl sulfoacid calcium 4-8
Part, (DDC)2Zn 5-12 part, chlorinated polyethylene 12-16 part, isoprene 12-16 part, amide waxe 14-23
Part, polybutylene terephthalate (PBT) fiber 9-15 part, dimethicone 8-13 part, carbon fiber 7-12 part, Fypro 4-6
Part, carboxyethyl cellulose 5-9 part, surfactant 0.6-1.2 part, initiator 0.4-0.6 part, chain extender 0.6-0.8 part, crosslinking
Agent 0.3-0.5 part, degasser 0.3-0.4 part, levelling agent 0.4-0.7 part, catalyst 0.2-0.4 part, accelerator 0.2-0.3 part,
Plasticizer 0.3-0.5 part, dispersant 0.2-0.4 part, viscosifier 0.3-0.4 part, firming agent 0.7-1.1 part, antibacterial 0.6-1.2
Part, antioxidant 0.4-0.6 part, light stabilizer 0.2-0.4 part, heat stabilizer 0.1-0.2 part, antiager 0.6-1.2 part, ultraviolet
Absorbent 0.4-0.6 part, fire retardant 1.2-1.5 part, smoke suppressant 0.5-0.8 part；
The dispersant is dispersant NC；
The viscosifier are butyl trimethoxy silane；
The firming agent is epoxylite firming agent；
The antibacterial 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 antiager;
The UV absorbent is oxybenzoic acid phenyl ester；
The fire retardant in units of weight portion, including following raw material：Ethylene glycol ether acetate 48-65 part, no phenyl ring oxygen tree
Fat 20-34 part, AESA 18-25 part, tripentaerythritol 12-22 part, carbamide 10-16 part, aluminium oxide
7-12 part, antimony oxide 9-12 part, manganese oxide 5-9 part, active hargil 8-12 part, penetrating agent 1.3-1.8 part, synergist 0.8-
1.2 part；
The smoke suppressant in units of weight portion, including following raw material：Tributyltin oxide 22-43 part, molybdenum hydroxide 12-20
Part, Kaolin 10-16 part, aluminium oxide 6-12 part, ammonium octamolybdate 4-7 part, stearic acid 1.2-2 part；
The preparation method of the high bending strength Graphene modified rubber material, comprises the following steps：
S1：Graphene is crushed, excessively 300-500 mesh sieve, prepared powder, gained powder is 5830-6250GS in magnetic field intensity,
Ultrasonic power is 350-480W, and it is under 200-300r/min that temperature is 42-53 DEG C, rotating speed, stirs 22-36min, prepared graphite
Alkene energy powder；
S2：Surfactant is added in Graphene energy powder obtained in step S1, be 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, to activate obtained in step S2 in Graphene energy powder add chlorohydrin rubber, neoprene,
Tributoxyethyl phosphate, dibutyl phthalate, three（2,4- di-tert-butyl-phenyls）Phosphite ester, stearyl acrylate acid
Ester, maleic anhydride grafting, magnesium hydroxide, Kaolin, white carbon black, cetyl sulfoacid calcium, (DDC)2Zn, chlorine
Change polyethylene, isoprene, amide waxe, polybutylene terephthalate (PBT) fiber, dimethicone, carbon fiber, polyamide fibre
Dimension, carboxyethyl cellulose, initiator, chain extender, cross-linking agent, degasser, levelling agent, catalyst, accelerator, plasticizer, dispersion
Agent, viscosifier, are 216-252W in microwave power, and it is to stir 3.4- under 300-500r/min that temperature is 127-133 DEG C, rotating speed
4.5h, prepared mixture I；
S4：Firming agent, antibacterial, antioxidant, light stabilizer, heat stabilizer, anti-ageing is added in mixture I obtained in step S3
Agent, UV absorbent, fire retardant, smoke suppressant, are 69-78 DEG C in temperature, and rotating speed is to stir 1-1.4 under 100-200r/min
H, prepared mixture II；
The preparation method of the fire retardant, comprises the following steps：
（a）AESA, water 240-300 part are added in microwave reactor, is 400- in speed of agitator
6-10min, prepared mixture A is stirred under 600r/min；
（b）Ethylene glycol ether acetate, no benzene epoxy resin, tripentaerythritol, urine is added in mixture A obtained in step a
Element, aluminium oxide, antimony oxide, manganese oxide, active hargil, penetrating agent, synergist, are 300-500r/min in speed of agitator,
Microwave power is 220-250W, and temperature stirs 2-2.5h, prepared mixture B at being 86-93 DEG C；
（c）Mixture B obtained in step b is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.4%, prepared fire retardant；
The preparation method of the smoke suppressant, comprises the following steps：
（A）By tributyltin oxide, molybdenum hydroxide, Kaolin, aluminium oxide, ammonium octamolybdate, stearic acid mixing, in speed of agitator it is
200-400r/min, microwave power is to stir 1.3-1.8h, prepared mixture C at 200-250W, temperature is 106-118 DEG C；
（B）Mixture C obtained in step A is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤2.8%, prepared smoke suppressant；
S5：Add in double screw extruder to mixture II obtained in step S4, be 224-235 DEG C in temperature, rotating speed is 400-
Melt extrude under conditions of 600r/min, by tank tie rod and pelletize in pelleter, prepared high bending strength Graphene changes
Property elastomeric material.
2. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the surface activity
Agent is surfactant TRITONCF-10.
3. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the initiator is
Dibenzoyl peroxide.
4. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the chain extender is
Methyl diphenylene diisocyanate.
5. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the cross-linking agent is
Methacrylamide.
6. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the degasser is
Stearic acid.
7. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the levelling agent is
Polyether polyester azo polyether polyeste.
8. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the catalyst is
Three（Dimethylamino-propyl）Hexahydrotriazine.
9. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the accelerator is
Colourless cobalt.
10. high bending strength Graphene modified rubber material according to claim 1, it is characterised in that the plasticizer
For citrate.
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| CN106751597A (en) * | 2017-03-27 | 2017-05-31 | 广西丰达三维科技有限公司 | Modified sheathing material of a kind of Graphene and preparation method thereof |
| CN106751630A (en) * | 2017-03-12 | 2017-05-31 | 广西丰达三维科技有限公司 | A kind of printing consumables with high impact-resistance and preparation method thereof |
| CN106832745A (en) * | 2017-03-27 | 2017-06-13 | 广西丰达三维科技有限公司 | A kind of preparation technology of the modified 3D printing material of Graphene |
| CN106883546A (en) * | 2017-03-27 | 2017-06-23 | 广西丰达三维科技有限公司 | A kind of modified environmentally friendly heat dissipation composite material of Graphene |
| CN106883570A (en) * | 2017-03-28 | 2017-06-23 | 广西丰达三维科技有限公司 | A kind of heat sink material with high tensile, preparation method and applications |
| CN106928666A (en) * | 2017-03-27 | 2017-07-07 | 广西丰达三维科技有限公司 | A kind of modified printing of Graphene radiating consumptive material and its application |
| CN107141546A (en) * | 2017-06-23 | 2017-09-08 | 广西南宁桂尔创环保科技有限公司 | 3D printing consumptive material prepared by a kind of high level cycling and reutilization waste rubber and preparation method thereof |
| CN107987475A (en) * | 2017-11-22 | 2018-05-04 | 新宇电缆集团股份有限公司 | A kind of highly effective flame-retardant high elongation rate cable jacket material |
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| CN106751630A (en) * | 2017-03-12 | 2017-05-31 | 广西丰达三维科技有限公司 | A kind of printing consumables with high impact-resistance and preparation method thereof |
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| CN106832745A (en) * | 2017-03-27 | 2017-06-13 | 广西丰达三维科技有限公司 | A kind of preparation technology of the modified 3D printing material of Graphene |
| CN106883546A (en) * | 2017-03-27 | 2017-06-23 | 广西丰达三维科技有限公司 | A kind of modified environmentally friendly heat dissipation composite material of Graphene |
| CN106928666A (en) * | 2017-03-27 | 2017-07-07 | 广西丰达三维科技有限公司 | A kind of modified printing of Graphene radiating consumptive material and its application |
| CN106883570A (en) * | 2017-03-28 | 2017-06-23 | 广西丰达三维科技有限公司 | A kind of heat sink material with high tensile, preparation method and applications |
| CN107141546A (en) * | 2017-06-23 | 2017-09-08 | 广西南宁桂尔创环保科技有限公司 | 3D printing consumptive material prepared by a kind of high level cycling and reutilization waste rubber and preparation method thereof |
| CN108690240A (en) * | 2017-06-23 | 2018-10-23 | 惠安县信达友工业设计有限公司 | A kind of fire retardant and preparation method thereof |
| CN107987475A (en) * | 2017-11-22 | 2018-05-04 | 新宇电缆集团股份有限公司 | A kind of highly effective flame-retardant high elongation rate cable jacket material |
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Application publication date: 20170222 |