CN106928742A - Modified plastic cement printing consumables of a kind of Graphene and preparation method thereof - Google Patents

Modified plastic cement printing consumables of a kind of Graphene and preparation method thereof Download PDF

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Publication number
CN106928742A
CN106928742A CN201710185796.6A CN201710185796A CN106928742A CN 106928742 A CN106928742 A CN 106928742A CN 201710185796 A CN201710185796 A CN 201710185796A CN 106928742 A CN106928742 A CN 106928742A
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parts
graphene
agent
plastic cement
modified
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冯可发
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Guangxi Feng Da Three Dimensional Technology Co Ltd
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Guangxi Feng Da Three Dimensional Technology Co Ltd
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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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/14—Footwear characterised by the material made of plastics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

A kind of plastic cement printing consumables being modified the invention discloses Graphene and preparation method thereof, the modified plastic cement printing consumables of the Graphene includes following raw material：Graphene, waste plastic, maleic anhydride is grafted ethylene propylene diene rubber, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2 hydroxyl, 4 octyloxy two, cyclobutenyl bis-stearamides, ethylene glycol monostearate, tributoxyethyl phosphate, three (2, 4 di-tert-butyl-phenyls) phosphite ester, surfactant, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant, the modified plastic cement printing consumables of the Graphene is through over cleaning, drying, crush, activation, mixing, what the steps such as extruding were made.The wearability and tensile strength of the modified plastic cement printing consumables of obtained Graphene of the invention are substantially better than the plastic material of prior art.

Description

Modified plastic cement printing consumables of a kind of Graphene and preparation method thereof
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of modified plastic cement printing consumption of Graphene Material and preparation method thereof.
【Background technology】
3D printing is also called 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, successively printed using the material with adhesion such as metal dust or plastics 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 is most difficult to most crucial technology Print the exploitation of material.Therefore developing more various multi-functional 3D printing material turns into focus of the future studies with application and pass Key.
The Geim and Novoselov of Man Chesidun universities of Britain in 2004 peel off high starch breeding and obtain solely by adhesive tape Since vertical two-dimensional graphene (Gra-phene, GN) crystal for existing, 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 at present it is most thin in the world be but also most hard nano material, it is almost fully transparent, to inhale 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 The new material of the individual layer laminated structure of composition, high with intensity, specific surface area is big, chemical reactivity high, the spy of fillibility high Point.
White pollution is the environmental pollution that global urban has, and can see what is largely discarded everywhere in various public places Plastic products, they come from nature, are manufactured by the mankind, are but difficult to be dissolved by natural when being finally attributed to the Nature, from And have impact on the ecological environment of the Nature.From the angle for economizing on resources, because plastic products main source is to face exhaustion Petroleum resources, should reclaim as far as possible, but because the production cost of recycling at this stage is far above direct production cost, existing It is difficult under condition of market economy.Therefore, how waste plastic is processed, becomes a kind of problem.
【The content of the invention】
The present invention provides modified plastic cement printing consumables of a kind of Graphene and preparation method thereof, to solve waste plastic treatment Problem.The wearability and tensile strength of the modified plastic cement printing consumables of obtained Graphene of the invention are substantially better than prior art Plastic material, while during plastic material of the invention can be applied to 3D printing article of footwear.
To solve above technical problem, the present invention uses following technical scheme：
A kind of modified plastic cement printing consumables of Graphene, in units of weight portion, including following raw material：Graphene 2.1- 4.4 parts, waste plastic 60-115 parts, maleic anhydride grafting 34-80 parts of ethylene propylene diene rubber, PLA 35-56 parts, tripolyphosphate Sodium 22-30 parts, phenyl propyl ketone 18-25 parts of 2- hydroxyl -4- octyloxies two, 20-32 parts of cyclobutenyl bis-stearamides, ethylene glycol list it is stearic Acid esters 10-15 parts, tributoxyethyl phosphate 15-20 parts, three phosphite ester 12-18 parts of (2,4- di-tert-butyl-phenyls), surface Activating agent 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant 0.4-0.6 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.6-1.2 Part, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, plasticizer 0.4-0.8 parts, dispersant 0.3-0.5 parts, tackifier 0.3- 0.6 part, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5 parts, stabilizer 0.2-0.4 parts, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 parts.
Preferably, the surfactant is Pluronic F68.
Preferably, the conditioning agent is ACR, and the propellant is aerogel generating agent, and the crosslinking agent is crosslinking agent SAC-100。
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.
Preferably, the fire retardant is in units of weight portion, including following raw material：Ethylene glycol ether acetate 60-68 parts, Miglyol 812N 25-28 parts, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, Urea 14-16 parts, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1- 2 parts；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 32-42 parts, lead hydroxide 16- 21 parts, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts.
The present invention also provides a kind of preparation method of the modified plastic cement printing consumables of Graphene, comprises the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, then will drying plastics and maleic anhydride grafting three 200-300 mesh sieve is crossed after first EP rubbers co-grinding, plastics powder is obtained；
S2：It it is 70-74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150- 1.2-1.8h is activated under 180r/min, activated plastics powder is obtained；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, 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 obtained；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2 Amount powder, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, phase Hold agent, bridging agent, catalyst, plasticizer, dispersant, tackifier, be 300-350W in microwave power, temperature is 138-145 DEG C, Rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4 Agent, is 76-80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/min；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature Under for 125-140r/min, through extruding strand, the modified plastic cement printing consumables of Graphene is obtained.
The invention has the advantages that：
(1), using conventional waste plastic, source is wide, and price is low, has widened the selection of 3D printing material feedstock for the present invention Scope, while for effective treatment of waste plastic provides new approach；
(2) wearability and tensile strength of the modified plastic cement printing consumables of the obtained Graphene of the present invention are substantially better than existing The plastic material of technology, adds Graphene to improve the intensity of plastic cement in plastic cement, and Graphene high lubricating effect can improve plastic cement Rub resistance；
(3) during plastic material of the invention can be applied to 3D printing article of footwear, and the plastic material of prior art can not be answered For in 3D printing article of footwear.
【Specific embodiment】
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to of the invention Protection domain, but do not limit the scope of the invention.
In embodiment, the modified plastic cement printing consumables of the Graphene, in units of weight portion, including following raw material： Graphene 2.1-4.4 parts, waste plastic 60-115 parts, maleic anhydride grafting 34-80 parts of ethylene propylene diene rubber, PLA 35-56 Part, sodium tripolyphosphate 22-30 parts, phenyl propyl ketone 18-25 parts of 2- hydroxyl -4- octyloxies two, 20-32 parts of cyclobutenyl bis-stearamides, Ethylene glycol monostearate 10-15 parts, tributoxyethyl phosphate 15-20 parts, three (2,4- di-tert-butyl-phenyl) phosphite esters 12-18 parts, surfactant 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant 0.4-0.6 parts, crosslinking agent 0.4-0.8 parts, phase Hold 0.6-1.2 parts of agent, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, plasticizer 0.4-0.8 parts, dispersant 0.3-0.5 Part, tackifier 0.3-0.6 parts, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5 parts, stabilizer 0.2-0.4 parts, antiager 1- 1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 parts；
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 weight portion, including following raw material：Ethylene glycol ether acetate 60-68 parts, the sad last of the ten Heavenly stems Acid glycerol three ester 25-28 parts, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14- 16 parts, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1-2 parts；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 32-42 parts, lead hydroxide 16- 21 parts, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts；
The preparation method of the modified plastic cement printing consumables of described Graphene, comprises the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, then will drying plastics and maleic anhydride grafting three 200-300 mesh sieve is crossed after first EP rubbers co-grinding, plastics powder is obtained；
S2：It it is 70-74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150- 1.2-1.8h is activated under 180r/min, activated plastics powder is obtained；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, 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 obtained；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2 Amount powder, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, phase Hold agent, bridging agent, catalyst, plasticizer, dispersant, tackifier, be 300-350W in microwave power, temperature is 138-145 DEG C, Rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4 Agent, is 76-80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, water 320-400 parts in microwave reactor, be in speed of agitator 8-12min is stirred under 300-500r/min, mixture A is obtained；
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in 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 temperature is obtained mixture B to stir 1.3-1.8h at 92-96 DEG C, and the bleeding agent is to ooze Saturating agent JFC；
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, be 4000-5000r/ in rotating speed Centrifugal drying is obtained fire retardant to water content≤1% 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 temperature is obtained mixture to stir 1-1.5h at 110-120 DEG C C；
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, is 4000-5000r/ in rotating speed Centrifugal drying is obtained smoke suppressant to water content≤1% under min；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature Under for 125-140r/min, through extruding strand, the modified plastic cement printing consumables of Graphene, the modified plastic cement of the Graphene is obtained Printing consumables is applied in 3D printing article of footwear.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of modified plastic cement printing consumables of Graphene, in units of weight portion, including following raw material：3.5 parts of Graphene, 90 parts of waste plastic, 60 parts of ethylene propylene diene rubber of maleic anhydride grafting, 45 parts of PLA, 26 parts of sodium tripolyphosphate, 2- hydroxyls -4- 22 parts of two phenyl propyl ketone of octyloxy, 26 parts of cyclobutenyl bis-stearamides, 13 parts of ethylene glycol monostearate, tributoxyethyl phosphate 18 parts, three 15 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 1.5 parts of surfactant, 0.8 part of conditioning agent, propellant 0.5 Part, 0.6 part of crosslinking agent, 1 part of compatilizer, 1 part of bridging agent, 0.5 part of catalyst, 0.6 part of plasticizer, 0.4 part of dispersant, tackifier 0.5 part, 1.8 parts of curing agent, 0.4 part of antioxidant, 0.3 part of stabilizer, 1.5 parts of antiager, 1.8 parts of fire retardant, 3 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 weight portion, 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 weight portion, 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 plastic cement printing consumables of described Graphene, comprises the following steps：
S1：It is 0.8% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three 200 mesh sieve are crossed after first EP rubbers co-grinding, plastics powder is obtained；
S2：It it is 72 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 170r/min Lower activation 1.5h, is obtained activated plastics powder；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7500GS in magnetic field intensity, Ultrasonic power is 600W, and temperature is 55 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 48min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2 Amount powder, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, phase Hold agent, bridging agent, catalyst, plasticizer, dispersant, tackifier, be 320W in microwave power, temperature is 142 DEG C, and rotating speed is 3.5h is stirred under 300r/min, mixture I is obtained；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4 Agent, is 78 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8h under 220r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, 350 parts of water in microwave reactor, be 400r/ in speed of agitator 10min is stirred under min, mixture A is obtained；
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in 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 temperature is obtained mixture B to stir 1.5h at 95 DEG C, and the bleeding agent is penetrating agent JFC；
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 4500r/min Centrifugal drying to water content is 1%, and fire retardant is obtained；
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 temperature is obtained mixture C to stir 1.3h at 110 DEG C；
(B) after mixture C obtained in step A being cooled into 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 obtained；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 195 DEG C in temperature, rotating speed is Under 135r/min, through extruding strand, the modified plastic cement printing consumables of Graphene, the modified plastic cement printing consumption of the Graphene is obtained Material is applied in 3D printing article of footwear.
Embodiment 2
A kind of modified plastic cement printing consumables of Graphene, in units of weight portion, including following raw material：2.2 parts of Graphene, 62 parts of waste plastic, 35 parts of ethylene propylene diene rubber of maleic anhydride grafting, 36 parts of PLA, 22 parts of sodium tripolyphosphate, 2- hydroxyls -4- 20 parts of two phenyl propyl ketone of octyloxy, 20 parts of cyclobutenyl bis-stearamides, 11 parts of ethylene glycol monostearate, tributoxyethyl phosphate 16 parts, three 12 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 1.3 parts of surfactant, 0.6 part of conditioning agent, propellant 0.4 Part, 0.4 part of crosslinking agent, 0.6 part of compatilizer, 0.6 part of bridging agent, 0.3 part of catalyst, 0.4 part of plasticizer, 0.3 part of dispersant, increasing 0.3 part of stick, 1.2 parts of curing agent, 0. part of antioxidant, 0.2 part of stabilizer, 1 part of antiager, 1.5 parts of fire retardant, 2 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 weight portion, 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 weight portion, 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 plastic cement printing consumables of described Graphene, comprises the following steps：
S1：It is 0.7% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three 200 mesh sieve are crossed after first EP rubbers co-grinding, plastics powder is obtained；
S2：It it is 70 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150r/min Lower activation 1.8h, is obtained activated plastics powder；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000GS in magnetic field intensity, Ultrasonic power is 520W, and temperature is 52 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 55min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2 Amount powder, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, phase Hold agent, bridging agent, catalyst, plasticizer, dispersant, tackifier, be 300W in microwave power, temperature is 138 DEG C, and rotating speed is 4h is stirred under 200r/min, mixture I is obtained；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4 Agent, is 76 DEG C in temperature, and rotating speed is obtained mixture II to stir 2h under 150r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, 320 parts of water in microwave reactor, be 300r/ in speed of agitator 12min is stirred under min, mixture A is obtained；
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in 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 temperature is obtained mixture B to stir 1.8h at 92 DEG C, and the bleeding agent is penetrating agent JFC；
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 4000r/min Centrifugal drying to water content is 0.8%, and fire retardant is obtained；
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 temperature is obtained mixture C to stir 1.5h at 110 DEG C；
(B) after mixture C obtained in step A being cooled into 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 obtained；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190 DEG C in temperature, rotating speed is Under 125r/min, through extruding strand, the modified plastic cement printing consumables of Graphene, the modified plastic cement printing consumption of the Graphene is obtained Material is applied in 3D printing article of footwear.
Embodiment 3
A kind of modified plastic cement printing consumables of Graphene, in units of weight portion, including following raw material：4.2 parts of Graphene, 113 parts of waste plastic, 78 parts of ethylene propylene diene rubber of maleic anhydride grafting, 55 parts of PLA, 30 parts of sodium tripolyphosphate, 2- hydroxyls- 24 parts of two phenyl propyl ketone of 4- octyloxies, 30 parts of cyclobutenyl bis-stearamides, 14 parts of ethylene glycol monostearate, tricresyl phosphate butoxy second 20 parts of ester, three 18 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 1.8 parts of surfactant, 1 part of conditioning agent, propellant 0.6 Part, 0.8 part of crosslinking agent, 1.2 parts of compatilizer, 1.2 parts of bridging agent, 0.6 part of catalyst, 0.8 part of plasticizer, 0.5 part of dispersant, increasing 0.6 part of stick, 2.5 parts of curing agent, 0.5 part of antioxidant, 0.4 part of stabilizer, 1.6 parts of antiager, 2 parts of fire retardant, smoke suppressant 4 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 weight portion, 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 weight portion, 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 plastic cement printing consumables of described Graphene, comprises the following steps：
S1：It is 0.6% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three 300 mesh sieve are crossed after first EP rubbers co-grinding, plastics powder is obtained；
S2：It it is 74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 180r/min Lower activation 1.2h, is obtained activated plastics powder；
S3：Graphene is crushed, 300 mesh sieve are crossed, powder is obtained, gained powder is 8200GS, ultrasound in magnetic field intensity Wave power is 650W, and temperature is 56 DEG C, and rotating speed is obtained Graphene energy powder under 300r/min, to stir 42min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2 Amount powder, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, phase Hold agent, bridging agent, catalyst, plasticizer, dispersant, tackifier, be 350W in microwave power, temperature is 145 DEG C, and rotating speed is 3h is stirred under 400r/min, mixture I is obtained；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4 Agent, is 80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6h under 250r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, 400 parts of water in microwave reactor, be 500r/ in speed of agitator 8min is stirred under min, mixture A is obtained；
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in 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 temperature is obtained mixture B to stir 1.3h at 96 DEG C, and the bleeding agent is penetrating agent JFC；
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 5000r/min Centrifugal drying to water content is 0.7%, and fire retardant is obtained；
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 temperature is obtained mixture C to stir 1h at 120 DEG C；
(B) after mixture C obtained in step A being cooled into 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 obtained；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 200 DEG C in temperature, rotating speed is Under 140r/min, through extruding strand, the modified plastic cement printing consumables of Graphene, the modified plastic cement printing consumption of the Graphene is obtained Material is applied in 3D printing article of footwear.
Comparative example 1, a kind of Patent Application Publication " environment friendly plastic rubber material (publication number：CN106084757A) " embodiment 3 is made The product for obtaining.
Comparative example 2, formula used is same as Example 3 with preparation method, and unique difference is not add Graphene wherein.
Plastic material prepared by plastic material and comparative example 1-2 prepared by detection embodiment 1-3, it is as a result as shown in the table：
Pilot project Wearability Tensile strength (MPa) In whether can be applied to 3D printing article of footwear
Embodiment 1 It is excellent 60.01 It is
Embodiment 2 It is excellent 56.34 It is
Embodiment 3 It is excellent 62.42 It is
Comparative example 1 It is good 46.35 It is no
Comparative example 2 It is good 51.16 It is
As seen from the above table, the wearability and tensile strength of the modified plastic cement printing consumables of the obtained Graphene of the present invention are obvious Better than the plastic material of comparative example 1-2.Graphene is added in plastic cement can improve the intensity of plastic cement, Graphene high lubricating effect, The rub resistance of plastic cement can be improved；In addition as can be seen from the above table, during product of the invention can be applied to 3D printing article of footwear, and The product of prior art may not apply in 3D printing article of footwear.
Above content is confined to these explanations it cannot be assumed that the present invention is embodied, 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 claims by being submitted to of the present invention determine.

Claims (10)

1. the plastic cement printing consumables that a kind of Graphene is modified, it is characterised in that in units of weight portion, including following raw material：Stone Black alkene 2.1-4.4 parts, waste plastic 60-115 parts, maleic anhydride grafting 34-80 parts of ethylene propylene diene rubber, PLA 35-56 parts, Sodium tripolyphosphate 22-30 parts, phenyl propyl ketone 18-25 parts of 2- hydroxyl -4- octyloxies two, 20-32 parts of cyclobutenyl bis-stearamides, second two 10-15 parts of alcohol monostearate, tributoxyethyl phosphate 15-20 parts, three (2,4- di-tert-butyl-phenyl) phosphite ester 12-18 Part, surfactant 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant 0.4-0.6 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.6-1.2 parts, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, plasticizer 0.4-0.8 parts, dispersant 0.3-0.5 parts, increasing Stick 0.3-0.6 parts, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5 parts, stabilizer 0.2-0.4 parts, antiager 1-1.6 parts, Fire retardant 1.5-2 parts, smoke suppressant 2-4 parts.
2. the modified plastic cement printing consumables of Graphene according to claim 1, it is characterised in that the surfactant is Pluronic F68.
3. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the conditioning agent is ACR, The propellant is aerogel generating agent, and the crosslinking agent is crosslinking aid S AC-100.
4. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the compatilizer is Malaysia Acid anhydrides is grafted compatilizer, and the bridging agent is acrylic type bridging agent.
5. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the catalyst is five oxygen Change two vanadium, the plasticizer is citrate.
6. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the dispersant is dispersion Agent MF, the tackifier are butyl trimethoxy silane.
7. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the curing agent is epoxy Resinoid curing agent, the antioxidant is antioxidant 1098.
8. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the stabilizer is modified Bentonite heat stabilizer, the antiager is BASF UV-234 antiagers.
9. the plastic cement printing consumables that Graphene according to claim 1 is modified, it is characterised in that the fire retardant is with weight Part it is unit, including following raw material：Ethylene glycol ether acetate 60-68 parts, Miglyol 812N 25-28 parts, nonyl phenol Polyoxyethylene ether ammonium sulfate 22-24 parts, 18-22 parts of PPOX triol, urea 14-16 parts, aluminum oxide 10-12 parts, three oxygen Change two antimony 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1-2 parts；
The smoke suppressant is in units of weight portion, including following raw material：Tributyltin oxide 32-42 parts, lead hydroxide 16-21 Part, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts.
10. the preparation method of the modified plastic cement printing consumables of Graphene according to claim any one of 1-9, its feature exists In comprising the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, then will drying plastics and maleic anhydride grafting ternary second Third rubber mix crosses 200-300 mesh sieve after crushing, and plastics powder is obtained；
S2：It it is 70-74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150-180r/ 1.2-1.8h is activated under min, activated plastics powder is obtained；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000-8200GS in magnetic field intensity, Ultrasonic power is 520-650W, and temperature is 52-56 DEG C, and rotating speed is obtained graphite under 200-300r/min, to stir 42-55min Alkene energy powder；
S4：Under nitrogen protection, to Graphene energy powder obtained in addition step S3 in activation plastics powder obtained in step S2 End, PLA, sodium tripolyphosphate, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol monostearate Ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, conditioning agent, propellant, crosslinking agent, compatilizer, Bridging agent, catalyst, plasticizer, dispersant, tackifier, are 300-350W in microwave power, and temperature is 138-145 DEG C, rotating speed To stir 3-4h under 200-400r/min, mixture I is obtained；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant in mixture I obtained in step S4, It it is 76-80 DEG C in temperature, rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/min；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C in temperature, rotating speed is Under 125-140r/min, through extruding strand, the modified plastic cement printing consumables of Graphene is obtained.
CN201710185796.6A 2017-03-26 2017-03-26 Modified plastic cement printing consumables of a kind of Graphene and preparation method thereof Pending CN106928742A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086983A (en) * 2014-07-28 2014-10-08 北京中科博益科技有限公司 Graphene/nylon composite material as well as preparation method and application of graphene/nylon composite material
CN106046755A (en) * 2016-07-29 2016-10-26 佛山市高明区诚睿基科技有限公司 Polyurethane composite material for 3D (three-dimensional) printing
CN106496983A (en) * 2016-11-17 2017-03-15 南宁梦幻三体环保科技有限公司 A kind of graphene composite material of 3D printing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086983A (en) * 2014-07-28 2014-10-08 北京中科博益科技有限公司 Graphene/nylon composite material as well as preparation method and application of graphene/nylon composite material
CN106046755A (en) * 2016-07-29 2016-10-26 佛山市高明区诚睿基科技有限公司 Polyurethane composite material for 3D (three-dimensional) printing
CN106496983A (en) * 2016-11-17 2017-03-15 南宁梦幻三体环保科技有限公司 A kind of graphene composite material of 3D printing

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Application publication date: 20170707