CN107043478A - A kind of application of modified rubber - Google Patents
A kind of application of modified rubber Download PDFInfo
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- CN107043478A CN107043478A CN201710340010.3A CN201710340010A CN107043478A CN 107043478 A CN107043478 A CN 107043478A CN 201710340010 A CN201710340010 A CN 201710340010A CN 107043478 A CN107043478 A CN 107043478A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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Abstract
The invention discloses a kind of application of modified rubber, belong to 3D printing technical field of material, the modified rubber includes following raw material：Graphene, waste rubber, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2 hydroxyl, 4 octyloxy two, cyclobutenyl bis-stearamides, PBT resin, stearyl acrylate acid esters, three (2,4 di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, surfactant, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant.The wearability and tensile strength of modified rubber produced by the present invention are substantially better than the elastomeric material of prior art, while the elastomeric material of the present invention can be applied in 3D printing tire product.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of application of modified rubber.
【Background technology】
3D printing is also known as rapid shaping technique, also referred to as increases material manufacturing technology, is that one kind does not need conventional tool, fixture
And lathe, but based on mathematical model file, the material for having adhesion using metal dust or rubber etc. is successively printed
To manufacture the technology of arbitrary shape article.The article that 3D printer can be manufactured is a lot, such as aircraft, pistol, for another example food, human body
Organ, toy for children etc..3D printing technique is an important breakthrough of world's manufacturing technology field over the past two decades.It is mechanic
The multidisciplinary technology such as journey, computer technology, Numeric Control Technology, material science it is integrated.It is to beat that 3D printing, which is most difficult to most crucial technology,
Print the exploitation of material.Therefore the more various multi-functional 3D printing material of exploitation turns into focus and pass of the future studies with application
Key.
The Geim and Novoselov of Man Chesidun universities of Britain in 2004 peel off high starch breeding by adhesive tape and obtained solely
Since vertical two-dimensional graphene (Gra-phene, GN) crystal existed, it is extremely concerned that graphene has become materials science field
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 at present it is most thin in the world be but also most hard nano material, it is almost fully transparent, to inhale
The light of receipts 2.3%, thermal conductivity factor is up to 5300W/mk, higher than CNT and diamond.Graphene is one kind by carbon atom
The new material of the individual layer laminated structure of composition, high with intensity, specific surface area is big, high chemical reactivity, the spy of high fillibility
Point.
In the culturally advanced and highly developed new century, one of serious problems that people face are waste treatment problems.
In order to meet the material performance requirement of continuous improvement, rubber develops towards high-strength, wear-resisting, stable and ageing-resistant direction, but together
When cause it is discarded after rubber the problem of be unable to natural degradation for a long time, such as largely discarded tire causes and compares plastic pollution
(white pollution) more intractable black pollution.In this way, on the one hand causing the serious infringement to environment, on the other hand waste
Valuable rubber sources.Therefore reclaim the rubber with regenerating waste, it is possible to reduce the regeneration of the pollution to environment, especially rubber,
Substantial amounts of rubber sources can be saved.When people are helplessly burned in face of the waste rubber product that pile up like a mountain in the presence of fuel
When, also seeking other solution routes.Therefore, how waste rubber is handled, becomes a kind of problem.
【The content of the invention】
The present invention provides a kind of application of modified rubber, to solve the problem of waste rubber is handled.It is produced by the present invention to change
Property rubber wearability and tensile strength be substantially better than the elastomeric material of prior art, while the elastomeric material of the present invention can be applied
In 3D printing tire product.
To solve above technical problem, the present invention uses following technical scheme：
A kind of application of modified rubber in 3D printing tire product.
Preferably, the modified rubber is in units of parts by weight, including following raw material：1.6-3.8 parts of graphene, discarded rubber
72-135 parts of glue, 32-50 parts of PLA, 30-42 parts of two polyphosphate sodium, 15-22 parts of two phenyl propyl ketone of 2- hydroxyl -4- octyloxies, fourth
18-30 parts of alkenyl bis-stearamides, 6-12 parts of PBT resin, 12-18 parts of stearyl acrylate acid esters, three (2,4- di-tert-butyls
Base) 9-15 parts of phosphite ester, 7-12 parts of polyimide fiber, 6-9 parts of carbon fiber, 1-1.6 parts of surfactant, conditioning agent 0.5-
0.9 part, 0.4-0.6 parts of propellant, 0.4-0.7 parts of crosslinking agent, 0.5-1 parts of compatilizer, 0.6-1.2 parts of bridging agent, catalyst
0.2-0.4 parts, 0.4-0.8 parts of plasticizer, 0.3-0.6 parts of dispersant, 0.4-0.6 parts of tackifier, 1-2.2 parts of curing agent, antioxygen
0.2-0.4 parts of agent, 0.3-0.5 parts of stabilizer, 0.8-1.2 parts of antiager, 1.4-1.8 parts of fire retardant, 1.7-3.5 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The fire retardant is in units of parts by weight, including following raw material：60-68 parts of ethylene glycol ether acetate, the sad last of the ten Heavenly stems
25-28 parts of acid glycerol three ester, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14-
16 parts, 10-12 parts of aluminum oxide, 9-11 parts of antimony oxide, 7-10 parts of lead oxide, 8-12 parts of bentonite, 1-2 parts of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：32-42 parts of tributyltin oxide, lead hydroxide 16-
21 parts, 12-20 parts of diatomite, 8-10 parts of aluminium hydroxide, 4-6 parts of ammonium octamolybdate, 1.5-2 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：Dried after waste rubber is cleaned to water content≤0.8%, then will cross 200-300 after drying rubber pulverizing
Mesh sieve, is made rubber powder；
S2：Surfactant is added into rubber powder made from step S1, is 72-78 DEG C in temperature, rotating speed is 140-
1-2h is activated under 200r/min, activating rubber powder end is made；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is made, gained powder is 7000- in magnetic field intensity
8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-55min,
Graphene energy powder is made；
S4：Under nitrogen protection, graphene energy made from step S3 is added into activating rubber powder end made from step S2
Measure powder, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, third
Olefin(e) acid stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant,
Crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 320-380W in microwave power, temperature is
142-146 DEG C, mixture I is made to stir 2.5-3.6h under 200-400r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette are added into mixture I made from step S4
Agent, is 73-82 DEG C in temperature, mixture II is made to stir 1.8-2.2h under 160-240r/min in rotating speed；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature
For under 130-140r/min, through extruding strand, modified rubber is made.
Preferably, the compatilizer is that maleic anhydride is grafted compatilizer, and the bridging agent is acrylic type bridging agent.
Preferably, the catalyst is vanadic anhydride, and the plasticizer is citrate.
Preferably, the dispersant is Dispersant MF, and the tackifier are butyl trimethoxy silane.
Preferably, the curing agent is epoxylite curing agent, and the antioxidant is antioxidant 1098.
Preferably, the stabilizer is modified alta-mud heat stabilizer, and the antiager is BASF UV-234 antiagers.
The invention has the advantages that：
(1) present invention is using conventional waste rubber, and source is wide, and price is low, has widened the selection of 3D printing material feedstock
Scope, while providing new approach for effective processing of waste rubber；
(2) wearability and tensile strength of modified rubber produced by the present invention are substantially better than the elastomeric material of prior art
(denomination of invention：A kind of high bending strength graphene modified rubber material, publication number：CN106433083A), added in rubber
Graphene can improve the intensity of rubber, graphene high lubricating effect, therefore can improve the rub resistance of rubber；Polyimide fiber
Addition with carbon fiber can cause the wearability of rubber to significantly improve, and improve the corrosion resistance of rubber so that the rub resistance of rubber
Performance increase；
(3) elastomeric material of the invention can be applied in 3D printing tire product, and the elastomeric material of prior art can not
Applied in 3D printing tire product.
【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 modified rubber, in units of parts by weight, including following raw material：1.6-3.8 parts of graphene,
72-135 parts of waste rubber, 32-50 parts of PLA, 30-42 parts of two polyphosphate sodium, the phenyl propyl ketone 15-22 of 2- hydroxyl -4- octyloxies two
Part, 18-30 parts of cyclobutenyl bis-stearamides, 6-12 parts of PBT resin, 12-18 parts of stearyl acrylate acid esters, three (2,4- bis- tertiary fourths
Base phenyl) 9-15 parts of phosphite ester, 7-12 parts of polyimide fiber, 6-9 parts of carbon fiber, 1-1.6 parts of surfactant, conditioning agent
0.5-0.9 parts, 0.4-0.6 parts of propellant, 0.4-0.7 parts of crosslinking agent, 0.5-1 parts of compatilizer, 0.6-1.2 parts of bridging agent, catalysis
It is 0.2-0.4 parts of agent, 0.4-0.8 parts of plasticizer, 0.3-0.6 parts of dispersant, 0.4-0.6 parts of tackifier, 1-2.2 parts of curing agent, anti-
0.2-0.4 parts of oxygen agent, 0.3-0.5 parts of stabilizer, 0.8-1.2 parts of antiager, 1.4-1.8 parts of fire retardant, smoke suppressant 1.7-3.5
Part；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
The stabilizer is modified alta-mud heat stabilizer；
The antiager is BASF UV-234 antiagers；
The fire retardant is in units of parts by weight, including following raw material：60-68 parts of ethylene glycol ether acetate, the sad last of the ten Heavenly stems
25-28 parts of acid glycerol three ester, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14-
16 parts, 10-12 parts of aluminum oxide, 9-11 parts of antimony oxide, 7-10 parts of lead oxide, 8-12 parts of bentonite, 1-2 parts of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：32-42 parts of tributyltin oxide, lead hydroxide 16-
21 parts, 12-20 parts of diatomite, 8-10 parts of aluminium hydroxide, 4-6 parts of ammonium octamolybdate, 1.5-2 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：Dried after waste rubber is cleaned to water content≤0.8%, then will cross 200-300 after drying rubber pulverizing
Mesh sieve, is made rubber powder；
S2：Surfactant is added into rubber powder made from step S1, is 72-78 DEG C in temperature, rotating speed is 140-
1-2h is activated under 200r/min, activating rubber powder end is made；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is made, gained powder is 7000- in magnetic field intensity
8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-55min,
Graphene energy powder is made；
S4：Under nitrogen protection, graphene energy made from step S3 is added into activating rubber powder end made from step S2
Measure powder, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, third
Olefin(e) acid stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant,
Crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 320-380W in microwave power, temperature is
142-146 DEG C, mixture I is made to stir 2.5-3.6h under 200-400r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette are added into mixture I made from step S4
Agent, is 73-82 DEG C in temperature, mixture II is made to stir 1.8-2.2h under 160-240r/min in rotating speed；
The preparation method of the fire retardant, comprises the following steps：
(a) NPE ammonium sulfate, 320-400 parts of water are added in microwave reactor, is in speed of agitator
8-12min is stirred under 300-500r/min, mixture A is made；
(b) ethylene glycol ether acetate, Miglyol 812N, polyoxygenated are added into mixture A made from step a
Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200-400r/ in speed of agitator
Min, microwave power is 350-400W, and mixture B is made to stir 1.3-1.8h at 92-96 DEG C in temperature, and the bleeding agent is to ooze
Saturating agent JFC；
(c) mixture B made from step b is cooled to after room temperature, sediment is filtered, be 4000-5000r/ in rotating speed
Fire retardant is made to water content≤1% in centrifugal drying under min；
The preparation method of the smoke suppressant, comprises the following steps：
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring
Rotating speed is 300-400r/min, and microwave power is 200-250W, and mixture is made to stir 1-1.5h at 110-120 DEG C in temperature
C；
(B) mixture C made from step A is cooled to after room temperature, sediment is filtered, be 4000-5000r/ in rotating speed
Smoke suppressant is made to water content≤1% in centrifugal drying under min；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature
Under 130-140r/min, through extruding strand, modified rubber to be made, the modified rubber is applied in 3D printing tire product.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of modified rubber, in units of parts by weight, including following raw material：It is 2.8 parts of graphene, 102 parts of waste rubber, poly-
42 parts of lactic acid, 35 parts of two polyphosphate sodium, 18 parts of two phenyl propyl ketone of 2- hydroxyl -4- octyloxies, 25 parts of cyclobutenyl bis-stearamides, PBT
9 parts of resin, 15 parts of stearyl acrylate acid esters, three 12 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 10 parts of polyimide fiber,
8 parts of carbon fiber, 1.3 parts of surfactant, 0.7 part of conditioning agent, 0.5 part of propellant, 0.6 part of crosslinking agent, 0.8 part of compatilizer, frame
0.9 part of bridge agent, 0.3 part of catalyst, 0.6 part of plasticizer, 0.5 part of dispersant, 0.5 part of tackifier, 1.6 parts of curing agent, antioxidant
0.3 part, 0.4 part of stabilizer, 1 part of antiager, 1.6 parts of fire retardant, 2.5 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
The stabilizer is modified alta-mud heat stabilizer；
The antiager is BASF UV-234 antiagers；
The fire retardant is in units of parts by weight, including following raw material：65 parts of ethylene glycol ether acetate, caprylic capric are sweet
Oily 27 parts of three ester, 23 parts of NPE ammonium sulfate, 20 parts of PPOX triol, 15 parts of urea, 11 parts of aluminum oxide,
10 parts of antimony oxide, 8 parts of lead oxide, 10 parts of bentonite, 1.6 parts of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：38 parts of tributyltin oxide, 18 parts of lead hydroxide,
16 parts of diatomite, 9 parts of aluminium hydroxide, 5 parts of ammonium octamolybdate, 1.8 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：It is 0.8% to be dried after waste rubber is cleaned to water content, then will drying rubber and maleic anhydride grafting three
200 mesh sieve are crossed after first EP rubbers co-grinding, rubber powder is made；
S2：Surfactant is added into rubber powder made from step S1, is 76 DEG C in temperature, rotating speed is 180r/min
Lower activation 1.5h, is made activating rubber powder end；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is made, gained powder is 7500GS in magnetic field intensity,
Ultrasonic power is 600W, and temperature is 55 DEG C, and graphene energy powder is made under 200r/min, to stir 48min in rotating speed；
S4：Under nitrogen protection, graphene energy made from step S3 is added into activating rubber powder end made from step S2
Measure powder, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, third
Olefin(e) acid stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant,
Crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 350W in microwave power, temperature is 145
DEG C, mixture I is made to stir 3h under 300r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette are added into mixture I made from step S4
Agent, is 78 DEG C in temperature, mixture II is made to stir 2h under 200r/min in rotating speed；
The preparation method of the fire retardant, comprises the following steps：
(a) NPE ammonium sulfate, 350 parts of water are added in microwave reactor, is 400r/ in speed of agitator
10min is stirred under min, mixture A is made；
(b) ethylene glycol ether acetate, Miglyol 812N, polyoxygenated are added into mixture A made from step a
Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 300r/min in speed of agitator, micro-
Wave power is 380W, and mixture B is made to stir 1.5h at 95 DEG C in temperature, and the bleeding agent is penetrating agent JFC；
(c) mixture B made from step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 4500r/min
Centrifugal drying to water content is 1%, and fire retardant is made；
The preparation method of the smoke suppressant, comprises the following steps：
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring
Rotating speed is 300r/min, and microwave power is 220W, and mixture C is made to stir 1.3h at 110 DEG C in temperature；
(B) mixture C made from step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 4500r/min
Centrifugal drying to water content is 1%, and smoke suppressant is made；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 195 DEG C in temperature, rotating speed is
Under 135r/min, through extruding strand, modified rubber is made, the modified rubber is applied in 3D printing tire product.
Embodiment 2
A kind of modified rubber, in units of parts by weight, including following raw material：It is 1.7 parts of graphene, 75 parts of waste rubber, poly-
32 parts of lactic acid, 30 parts of two polyphosphate sodium, 16 parts of two phenyl propyl ketone of 2- hydroxyl -4- octyloxies, 18 parts of cyclobutenyl bis-stearamides, PBT
6 parts of resin, 12 parts of stearyl acrylate acid esters, three 9 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 7 parts of polyimide fiber, carbon
6 parts of fiber, 1 part of surfactant, 0.5 part of conditioning agent, 0.4 part of propellant, 0.4 part of crosslinking agent, 0.5 part of compatilizer, bridging agent
0.6 part, 0.2 part of catalyst, 0.4 part of plasticizer, 0.3 part of dispersant, 0.4 part of tackifier, 1 part of curing agent, 0.2 part of antioxidant,
0.3 part of stabilizer, 0.8 part of antiager, 1.4 parts of fire retardant, 1.7 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
The stabilizer is modified alta-mud heat stabilizer；
The antiager is BASF UV-234 antiagers；
The fire retardant is in units of parts by weight, including following raw material：62 parts of ethylene glycol ether acetate, caprylic capric are sweet
Oily 25 parts of three ester, 22 parts of NPE ammonium sulfate, 18 parts of PPOX triol, 14 parts of urea, 10 parts of aluminum oxide,
9 parts of antimony oxide, 7 parts of lead oxide, 8 parts of bentonite, 1 part of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：34 parts of tributyltin oxide, 16 parts of lead hydroxide,
12 parts of diatomite, 8 parts of aluminium hydroxide, 4 parts of ammonium octamolybdate, 1.6 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：It is 0.7% to be dried after waste rubber is cleaned to water content, then will drying rubber and maleic anhydride grafting three
200 mesh sieve are crossed after first EP rubbers co-grinding, rubber powder is made；
S2：Surfactant is added into rubber powder made from step S1, is 72 DEG C in temperature, rotating speed is 140r/min
Lower activation 2h, is made activating rubber powder end；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is made, gained powder is 7000GS in magnetic field intensity,
Ultrasonic power is 520W, and temperature is 52 DEG C, and graphene energy powder is made under 200r/min, to stir 55min in rotating speed；
S4：Under nitrogen protection, graphene energy made from step S3 is added into activating rubber powder end made from step S2
Measure powder, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, third
Olefin(e) acid stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant,
Crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 320W in microwave power, temperature is 142
DEG C, mixture I is made to stir 3.6h under 200r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette are added into mixture I made from step S4
Agent, is 73 DEG C in temperature, mixture II is made to stir 2.2h under 160r/min in rotating speed；
The preparation method of the fire retardant, comprises the following steps：
(a) NPE ammonium sulfate, 320 parts of water are added in microwave reactor, is 300r/ in speed of agitator
12min is stirred under min, mixture A is made；
(b) ethylene glycol ether acetate, Miglyol 812N, polyoxygenated are added into mixture A made from step a
Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200r/min in speed of agitator, micro-
Wave power is 350W, and mixture B is made to stir 1.8h at 92 DEG C in temperature, and the bleeding agent is penetrating agent JFC；
(c) mixture B made from step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 4000r/min
Centrifugal drying to water content is 0.8%, and fire retardant is made；
The preparation method of the smoke suppressant, comprises the following steps：
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring
Rotating speed is 300r/min, and microwave power is 200W, and mixture C is made to stir 1.5h at 110 DEG C in temperature；
(B) mixture C made from step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 4000r/min
Centrifugal drying to water content is 0.8%, and smoke suppressant is made；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 190 DEG C in temperature, rotating speed is
Under 130r/min, through extruding strand, modified rubber is made, the modified rubber is applied in 3D printing tire product.
Embodiment 3
A kind of modified rubber, in units of parts by weight, including following raw material：It is 3.6 parts of graphene, 134 parts of waste rubber, poly-
49 parts of lactic acid, 42 parts of two polyphosphate sodium, 22 parts of two phenyl propyl ketone of 2- hydroxyl -4- octyloxies, 30 parts of cyclobutenyl bis-stearamides, PBT
12 parts of resin, 18 parts of stearyl acrylate acid esters, three 15 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber 12
Part, 9 parts of carbon fiber, 1.6 parts of surfactant, 0.9 part of conditioning agent, 0.6 part of propellant, 0.7 part of crosslinking agent, 1 part of compatilizer, frame
1.2 parts of bridge agent, 0.4 part of catalyst, 0.8 part of plasticizer, 0.6 part of dispersant, 0.6 part of tackifier, 2.2 parts of curing agent, antioxidant
0.4 part, 0.5 part of stabilizer, 1.2 parts of antiager, 1.8 parts of fire retardant, 3.5 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
The stabilizer is modified alta-mud heat stabilizer；
The antiager is BASF UV-234 antiagers；
The fire retardant is in units of parts by weight, including following raw material：68 parts of ethylene glycol ether acetate, caprylic capric are sweet
Oily 28 parts of three ester, 24 parts of NPE ammonium sulfate, 22 parts of PPOX triol, 16 parts of urea, 12 parts of aluminum oxide,
11 parts of antimony oxide, 10 parts of lead oxide, 12 parts of bentonite, 2 parts of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：42 parts of tributyltin oxide, 21 parts of lead hydroxide,
20 parts of diatomite, 10 parts of aluminium hydroxide, 6 parts of ammonium octamolybdate, 2 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：It is 0.6% to be dried after waste rubber is cleaned to water content, then will drying rubber and maleic anhydride grafting three
300 mesh sieve are crossed after first EP rubbers co-grinding, rubber powder is made；
S2：Surfactant is added into rubber powder made from step S1, is 78 DEG C in temperature, rotating speed is 200r/min
Lower activation 1h, is made activating rubber powder end；
S3：Graphene is crushed, 300 mesh sieve are crossed, powder is made, gained powder is 8200GS, ultrasound in magnetic field intensity
Wave power is 650W, and temperature is 56 DEG C, and graphene energy powder is made under 300r/min, to stir 42min in rotating speed；
S4：Under nitrogen protection, graphene energy made from step S3 is added into activating rubber powder end made from step S2
Measure powder, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, third
Olefin(e) acid stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant,
Crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 380W in microwave power, temperature is 146
DEG C, mixture I is made to stir 2.5h under 400r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette are added into mixture I made from step S4
Agent, is 73 DEG C in temperature, mixture II is made to stir 2.2h under 160r/min in rotating speed；
The preparation method of the fire retardant, comprises the following steps：
(a) NPE ammonium sulfate, 400 parts of water are added in microwave reactor, is 500r/ in speed of agitator
8min is stirred under min, mixture A is made；
(b) ethylene glycol ether acetate, Miglyol 812N, polyoxygenated are added into mixture A made from step a
Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 400r/min in speed of agitator, micro-
Wave power is 400W, and mixture B is made to stir 1.3h at 96 DEG C in temperature, and the bleeding agent is penetrating agent JFC；
(c) mixture B made from step b is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 5000r/min
Centrifugal drying to water content is 0.7%, and fire retardant is made；
The preparation method of the smoke suppressant, comprises the following steps：
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring
Rotating speed is 400r/min, and microwave power is 250W, and mixture C is made to stir 1h at 120 DEG C in temperature；
(B) mixture C made from step A is cooled to after room temperature, sediment is filtered, in the case where rotating speed is 5000r/min
Centrifugal drying to water content is 0.7%, and smoke suppressant is made；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 200 DEG C in temperature, rotating speed is
Under 140r/min, through extruding strand, modified rubber is made, the modified rubber is applied in 3D printing tire product.
Comparative example 1, a kind of Patent Application Publication " high bending strength graphene modified rubber material (publication number：
CN106433083A) " product made from embodiment 3.
Comparative example 2, formula used is same as Example 3 with preparation method, and unique difference is not add graphene wherein.
Comparative example 3, formula used is same as Example 3 with preparation method, and unique difference is not add polyimide fiber wherein
And carbon fiber.
Comparative example 4, formula used is same as Example 3 with preparation method, and unique difference is not add graphene, polyamides Asia wherein
Amine fiber and carbon fiber.
Detect that result is such as under elastomeric material prepared by the elastomeric material and comparative example 1-4 of embodiment 1-3 preparations, identical conditions
Shown in following table：
As seen from the above table, the wearability and tensile strength for the Environment-friendlywear-resistant wear-resistant elastomeric material that graphene produced by the present invention is modified
It is substantially better than comparative example 1-4 elastomeric material.Graphene is added in rubber can improve the intensity of rubber, graphene lubricant effect
It is good, the rub resistance of rubber can be improved；The addition of polyimide fiber and carbon fiber can cause the wearability of rubber significantly to carry
Height, improves the corrosion resistance of rubber so that the crocking resistance increase of rubber.In addition as can be seen from the above table, graphene, polyamides are sub-
The addition of amine fiber and carbon fiber serves synergy, is conducive to increasing wearability.The product of the present invention can be applied to 3D and beat
Print in tire product, and the product of prior art may not apply in 3D printing tire product.
Above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of present inventive concept is not departed from, some simple deduction or replace can also be made, all should
When being considered as belonging to the scope of patent protection that is determined by the claims submitted of the present invention.
Claims (7)
1. a kind of application of modified rubber in 3D printing tire product.
2. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the modified rubber
Glue is in units of parts by weight, including following raw material：1.6-3.8 parts of graphene, 72-135 parts of waste rubber, 32-50 parts of PLA,
Two 30-42 parts of polyphosphate sodiums, 15-22 parts of two phenyl propyl ketone of 2- hydroxyl -4- octyloxies, 18-30 parts of cyclobutenyl bis-stearamides, PBT
6-12 parts of resin, 12-18 parts of stearyl acrylate acid esters, three 9-15 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, polyimides
7-12 parts of fiber, 6-9 parts of carbon fiber, 1-1.6 parts of surfactant, 0.5-0.9 parts of conditioning agent, 0.4-0.6 parts of propellant, crosslinking
0.4-0.7 parts of agent, 0.5-1 parts of compatilizer, 0.6-1.2 parts of bridging agent, 0.2-0.4 parts of catalyst, 0.4-0.8 parts of plasticizer, point
0.3-0.6 parts of powder, 0.4-0.6 parts of tackifier, 1-2.2 parts of curing agent, 0.2-0.4 parts of antioxidant, 0.3-0.5 parts of stabilizer,
0.8-1.2 parts of antiager, 1.4-1.8 parts of fire retardant, 1.7-3.5 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The fire retardant is in units of parts by weight, including following raw material：60-68 parts of ethylene glycol ether acetate, caprylic capric are sweet
Oily 25-28 parts of three ester, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14-16
Part, 10-12 parts of aluminum oxide, 9-11 parts of antimony oxide, 7-10 parts of lead oxide, 8-12 parts of bentonite, 1-2 parts of bleeding agent；
The smoke suppressant is in units of parts by weight, including following raw material：32-42 parts of tributyltin oxide, lead hydroxide 16-21
Part, 12-20 parts of diatomite, 8-10 parts of aluminium hydroxide, 4-6 parts of ammonium octamolybdate, 1.5-2 parts of stearic acid；
The preparation method of the modified rubber, comprises the following steps：
S1：Dried after waste rubber is cleaned to water content≤0.8%, then will cross 200-300 mesh sieves after drying rubber pulverizing
Son, is made rubber powder；
S2：Surfactant is added into rubber powder made from step S1, is 72-78 DEG C in temperature, rotating speed is 140-200r/
1-2h is activated under min, activating rubber powder end is made；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is made, gained powder is 7000-8200GS in magnetic field intensity,
Ultrasonic power is 520-650W, and temperature is 52-56 DEG C, and graphite is made under 200-300r/min, to stir 42-55min in rotating speed
Alkene energy powder；
S4：Under nitrogen protection, graphene energy powder made from step S3 is added into activating rubber powder end made from step S2
End, PLA, two polyphosphate sodiums, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, PBT resin, acrylic acid
Stearate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyimide fiber, carbon fiber, conditioning agent, propellant, crosslinking
Agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 320-380W in microwave power, temperature is 142-
146 DEG C, mixture I is made to stir 2.5-3.6h under 200-400r/min in rotating speed；
S5：Curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant are added into mixture I made from step S4,
It it is 73-82 DEG C in temperature, mixture II is made to stir 1.8-2.2h under 160-240r/min in rotating speed；
S6：Mixture II made from step S5 is put into screw extruding forming machine, is 190-200 DEG C in temperature, rotating speed is
Under 130-140r/min, through extruding strand, modified rubber is made.
3. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the compatilizer
Compatilizer is grafted for maleic anhydride, the bridging agent is acrylic type bridging agent.
4. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the catalyst
For vanadic anhydride, the plasticizer is citrate.
5. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the dispersant
For Dispersant MF, the tackifier are butyl trimethoxy silane.
6. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the curing agent
For epoxylite curing agent, the antioxidant is antioxidant 1098.
7. application of the modified rubber in 3D printing tire product according to claim 1, it is characterised in that the stabilizer
For modified alta-mud heat stabilizer, the antiager is BASF UV-234 antiagers.
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