CN106832745A - A kind of preparation technology of the modified 3D printing material of Graphene - Google Patents

A kind of preparation technology of the modified 3D printing material of Graphene Download PDF

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CN106832745A
CN106832745A CN201710189619.5A CN201710189619A CN106832745A CN 106832745 A CN106832745 A CN 106832745A CN 201710189619 A CN201710189619 A CN 201710189619A CN 106832745 A CN106832745 A CN 106832745A
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modified
graphene
agent
printing material
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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of preparation technology of the 3D printing material being modified the invention discloses Graphene, the modified 3D printing material of the Graphene includes following raw material：The steps such as Graphene, ABS resin, zinc acrylate resin, PLA, two polyphosphate sodiums, chloropropyl styrene, maleic anhydride inoculated polypropylene, sodium cellulose glycolate, Kafra fiber, polybutylene terephthalate (PBT) fiber, surfactant, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, curing agent, antioxidant, stabilizer, antiager, fire retardant, the modified 3D printing material of the Graphene is by crushing, activation, mixing, extruding are made.The thermal diffusivity and tensile strength of the modified 3D printing material of obtained Graphene of the invention are substantially better than the material of prior art；Meanwhile, material of the invention can be applied in 3D printing notebook computer casing.

Description

A kind of preparation technology of the modified 3D printing material of Graphene
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of modified 3D printing material of Graphene Preparation technology.
【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.
With the fast development of notebook computer industry, notebook computer casing also towards intensity it is high, rigidity is big, direction Development.Most plastic casing notebook computers is all to do raw material using PC/ABS engineering plastic alloys in the market.This The material both excellent heat-resisting weatherability with PC resin, dimensional stability and impact resistance are planted, but it is excellent with ABS resin Processing fluidity.But, there is a problem that the heat dispersion of notebook computer casing is poor.
【The content of the invention】
The present invention provides a kind of preparation technology of the modified 3D printing material of Graphene, to solve outside existing notebook computer The poor problem of the heat dispersion of shell.The thermal diffusivity and tensile strength of the modified 3D printing material of obtained Graphene of the invention are bright The aobvious material better than prior art；Meanwhile, material of the invention can be applied in 3D printing notebook computer casing.
To solve above technical problem, the present invention uses following technical scheme：
A kind of preparation technology of the modified 3D printing material of Graphene, comprises the following steps：
S1：200-300 mesh sieve is crossed after ABS resin 86-124 parts is crushed with zinc acrylate resin 24-38 parts, is obtained mixed Resin powder；
S2：It is 68-72 DEG C in temperature to 1-1.6 parts of surfactant is added in hybrid resin powder obtained in step S1, Rotating speed is obtained activation hybrid resin powder to activate 1-1.3h under 150-180r/min；
S3：By Graphene 1.8-4.2 parts of crushing, 200-300 mesh sieve is crossed, powder is obtained, gained powder is in magnetic field intensity It is 7000-8200GS, ultrasonic power is 520-650W, temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 40- 50min, is obtained Graphene energy powder；
S4：Under nitrogen protection, to graphite obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Alkene energy powder, PLA 54-76 parts, two polyphosphate sodium 46-62 parts, 12-16 parts of chloropropyl styrene, maleic anhydride grafting it is poly- Propylene 10-14 parts, sodium cellulose glycolate 8-12 parts, Kafra fiber 4-6 parts, polybutylene terephthalate (PBT) fiber 3-5 Part, conditioning agent 0.4-0.8 parts, propellant 0.3-0.5 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.7-1.3 parts, bridging agent 0.5- 1 part, catalyst 0.3-0.5 parts, plasticizer 0.5-0.8 parts, dispersant 0.3-0.5 parts, tackifier 0.4-0.7 parts, in microwave work( Rate is 300-350W, and temperature is 138-145 DEG C, and rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To 1-2.3 parts of curing agent of addition, antioxidant 0.3-0.5 parts, stabilizer in mixture I obtained in step S4 0.2-0.4 parts, antiager 1.2-1.8 parts, fire retardant 1.8-2.4 parts, be 76-80 DEG C in temperature, and rotating speed is 150-250r/min Lower stirring 1.6-2h, is obtained mixture II；
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 3D printing material of Graphene is obtained.
Preferably, surfactant described in step S2 is Pluronic F68.
Preferably, conditioning agent described in step S4 is ACR, and the propellant is aerogel generating agent.
Preferably, crosslinking agent described in step S4 is crosslinking aid S AC-100, and the compatilizer is that maleic anhydride grafting is compatible Agent.
Preferably, bridging agent described in step S4 is acrylic type bridging agent, and the catalyst is vanadic anhydride.
Preferably, plasticizer described in step S4 is citrate, and the dispersant is Dispersant MF, and the tackifier are Butyl trimethoxy silane.
Preferably, step S in step S4, curing agent described in 5 is epoxylite curing agent.
Preferably, step S in step S4, antioxidant described in 5 is antioxidant 2246, and the stabilizer is modified alta-mud Heat stabilizer.
In preferably step S4, step S, antiager described in 5 is BASF UV-234 antiagers.
Preferably, step S, fire retardant described in 5 is in units of weight portion, including following raw material：Ethylene glycol ethyl ether acetic acid Ester 60-68 parts, Miglyol 812N 25-28 parts, 22-24 parts of NPE ammonium sulfate, PPOX three Alcohol 18-22 parts, urea 14-16 parts, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 Part, bleeding agent 1-2 parts.
The invention has the advantages that：
The thermal diffusivity and tensile strength of the modified 3D printing material of obtained Graphene of the invention are substantially better than prior art Material.Meanwhile, material of the invention be can be applied in 3D printing notebook computer casing, and the material of prior art can not be answered For in 3D printing notebook computer casing.
【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 3D printing material of the Graphene, in units of weight portion, including following raw material：Stone Black alkene 1.8-4.2 parts, ABS resin 86-124 parts, zinc acrylate resin 24-38 parts, PLA 54-76 parts, two polyphosphate sodium 46- 62 parts, 12-16 parts of chloropropyl styrene, maleic anhydride inoculated polypropylene 10-14 parts, sodium cellulose glycolate 8-12 parts, Kev Tow dimension 4-6 parts, 3-5 parts of polybutylene terephthalate (PBT) fiber, surfactant 1-1.6 parts, conditioning agent 0.4-0.8 parts, Propellant 0.3-0.5 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.7-1.3 parts, bridging agent 0.5-1 parts, catalyst 0.3-0.5 Part, plasticizer 0.5-0.8 parts, dispersant 0.3-0.5 parts, tackifier 0.4-0.7 parts, curing agent 1-2.3 parts, antioxidant 0.3- 0.5 part, stabilizer 0.2-0.4 parts, antiager 1.2-1.8 parts, fire retardant 1.8-2.4 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 2246；
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 preparation method of the modified 3D printing material of described Graphene, comprises the following steps：
S1：200-300 mesh sieve is crossed after ABS resin and zinc acrylate resin are crushed, hybrid resin powder is obtained；
S2：It it is 68-72 DEG C in temperature to surfactant is added in hybrid resin powder obtained in step S1, rotating speed is 1-1.3h is activated under 150-180r/min, activation hybrid resin 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 40-50min, Graphene energy powder is obtained；
S4：Under nitrogen protection, to graphite obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Alkene energy powder, PLA, two polyphosphate sodiums, chloropropyl styrene, maleic anhydride inoculated polypropylene, sodium cellulose glycolate, Kafra fiber, polybutylene terephthalate (PBT) fiber, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalysis Agent, plasticizer, dispersant, tackifier, are 300-350W in microwave power, and temperature is 138-145 DEG C, and rotating speed is 200-400r/ 3-4h is stirred under min, mixture I is obtained；
S5：To curing agent, antioxidant, stabilizer, antiager, fire retardant is added in mixture I obtained in step S4, in temperature It is 76-80 DEG C to spend, 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；
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 3D printing material of Graphene, the modified 3D printing of the Graphene is obtained Materials application is in 3D printing notebook computer casing.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of modified 3D printing material of Graphene, in units of weight portion, including following raw material：3 parts of Graphene, ABS 106 parts of resin, 30 parts of zinc acrylate resin, 65 parts of PLA, 52 parts of two polyphosphate sodium, 15 parts of chloropropyl styrene, maleic acid 12 parts of acid anhydride graft polypropylene, 10 parts of sodium cellulose glycolate, 5 parts of Kafra fiber, polybutylene terephthalate (PBT) fiber 4 Part, 1.3 parts of surfactant, 0.6 part of conditioning agent, 0.4 part of propellant, 0.6 part of crosslinking agent, 1 part of compatilizer, 0.7 part of bridging agent, 0.4 part of catalyst, 0.7 part of plasticizer, 0.4 part of dispersant, 0.6 part of tackifier, 1.6 parts of curing agent, 0.4 part of antioxidant, stabilization 0.3 part of agent, 1.5 parts of antiager, 2 parts of fire retardant；
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 2246；
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, 9 parts of lead oxide, 10 parts of bentonite, 1.5 parts of bleeding agent；
The preparation method of the modified 3D printing material of described Graphene, comprises the following steps：
S1：2000 mesh sieve are crossed after ABS resin and zinc acrylate resin are crushed, hybrid resin powder is obtained；
S2：It it is 70 DEG C in temperature to surfactant is added in hybrid resin powder obtained in step S1, rotating speed is 1.2h is activated under 170r/min, activation hybrid resin powder is obtained；
S3：Graphene is crushed, 200 mesh sieve are crossed, powder is obtained, gained powder is 7500GS, ultrasound in magnetic field intensity Wave power is 600W, and temperature is 55 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 45min；
S4：Under nitrogen protection, to graphite obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Alkene energy powder, PLA, two polyphosphate sodiums, chloropropyl styrene, maleic anhydride inoculated polypropylene, sodium cellulose glycolate, Kafra fiber, polybutylene terephthalate (PBT) fiber, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalysis Agent, plasticizer, dispersant, tackifier, are 320W in microwave power, and temperature is 140 DEG C, and rotating speed is stirring under 300r/min 3.5h, is obtained mixture I；
S5：To curing agent, antioxidant, stabilizer, antiager, fire retardant is added in mixture I obtained in step S4, in temperature It is 78 DEG C to spend, and rotating speed is obtained mixture II to stir 1.8h under 200r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, 360 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 195 DEG C in temperature, rotating speed is Under 1350r/min, through extruding strand, the modified 3D printing material of Graphene, the modified 3D printing material of the Graphene is obtained It is applied in 3D printing notebook computer casing.
Embodiment 2
A kind of modified 3D printing material of Graphene, in units of weight portion, including following raw material：2 parts of Graphene, ABS 88 parts of resin, 25 parts of zinc acrylate resin, 55 parts of PLA, 46 parts of two polyphosphate sodium, 12 parts of chloropropyl styrene, maleic anhydride 10 parts of graft polypropylene, 8 parts of sodium cellulose glycolate, 4 parts of Kafra fiber, 3 parts of polybutylene terephthalate (PBT) fiber, table 1 part of face activating agent, 0.4 part of conditioning agent, 0.3 part of propellant, 0.4 part of crosslinking agent, 0.7 part of compatilizer, 0.5 part of bridging agent, catalysis 0.3 part of agent, 0.5 part of plasticizer, 0.3 part of dispersant, 0.4 part of tackifier, 1 part of curing agent, 0.3 part of antioxidant, stabilizer 0.2 Part, 1.2 parts of antiager, 1.8 parts of fire retardant；
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 2246；
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：60 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 preparation method of the modified 3D printing material of described Graphene, comprises the following steps：
S1：200 mesh sieve are crossed after ABS resin and zinc acrylate resin are crushed, hybrid resin powder is obtained；
S2：It it is 68 DEG C in temperature to surfactant is added in hybrid resin powder obtained in step S1, rotating speed is 1.3h is activated under 150r/min, activation hybrid resin powder is obtained；
S3：Graphene is crushed, 200 mesh sieve are crossed, powder is obtained, gained powder is 7000GS, ultrasound in magnetic field intensity Wave power is 520W, and temperature is 52 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 40min；
S4：Under nitrogen protection, to graphite obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Alkene energy powder, PLA, two polyphosphate sodiums, chloropropyl styrene, maleic anhydride inoculated polypropylene, sodium cellulose glycolate, Kafra fiber, polybutylene terephthalate (PBT) fiber, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalysis Agent, plasticizer, dispersant, tackifier, microwave power be 300W, temperature be 138 DEG C, rotating speed be 200r/min under stir 4h, Mixture I is obtained；
S5：To curing agent, antioxidant, stabilizer, antiager, fire retardant is added in mixture I obtained in step S4, in temperature It is 76 DEG C to spend, 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；
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 3D printing material of Graphene is obtained, the modified 3D printing material of the Graphene should For in 3D printing notebook computer casing.
Embodiment 3
A kind of modified 3D printing material of Graphene, in units of weight portion, including following raw material：4 parts of Graphene, ABS 122 parts of resin, 36 parts of zinc acrylate resin, 75 parts of PLA, 60 parts of two polyphosphate sodium, 16 parts of chloropropyl styrene, maleic acid 14 parts of acid anhydride graft polypropylene, 12 parts of sodium cellulose glycolate, 6 parts of Kafra fiber, polybutylene terephthalate (PBT) fiber 5 Part, 1.6 parts of surfactant, 0.8 part of conditioning agent, 0.5 part of propellant, 0.8 part of crosslinking agent, 1.3 parts of compatilizer, 1 part of bridging agent, 0.5 part of catalyst, 0.8 part of plasticizer, 0.5 part of dispersant, 0.7 part of tackifier, 2.3 parts of curing agent, 0.5 part of antioxidant, stabilization 0.4 part of agent, 1.8 parts of antiager, 2.4 parts of fire retardant；
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 2246；
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 preparation method of the modified 3D printing material of described Graphene, comprises the following steps：
S1：300 mesh sieve are crossed after ABS resin and zinc acrylate resin are crushed, hybrid resin powder is obtained；
S2：It it is 72 DEG C in temperature to surfactant is added in hybrid resin powder obtained in step S1, rotating speed is 1.3h is activated under 180r/min, activation hybrid resin powder is obtained；
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 40min；
S4：Under nitrogen protection, to graphite obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Alkene energy powder, PLA, two polyphosphate sodiums, chloropropyl styrene, maleic anhydride inoculated polypropylene, sodium cellulose glycolate, Kafra fiber, polybutylene terephthalate (PBT) fiber, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalysis Agent, plasticizer, dispersant, tackifier, microwave power be 350W, temperature be 145 DEG C, rotating speed be 400r/min under stir 3h, Mixture I is obtained；
S5：To curing agent, antioxidant, stabilizer, antiager, fire retardant is added in mixture I obtained in step S4, in temperature It is 80 DEG C to spend, 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 0.5%, and fire retardant 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 3D printing material of Graphene is obtained, the modified 3D printing material of the Graphene should For in 3D printing notebook computer casing.
Comparative example 1, a kind of Patent Application Publication " high-performance notebook computer casing composite (publication number：CN 106479136A) " product obtained in embodiment 3.
Comparative example 2, formula used is same as Example 3 with preparation method, and unique difference is not add Graphene wherein.
Material prepared by material and comparative example 1-2 prepared by detection embodiment 1-3, it is as a result as shown in the table：
As seen from the above table, the thermal diffusivity and tensile strength of the modified 3D printing material of the obtained Graphene of the present invention are substantially excellent In the material of comparative example 1-2.In addition as can be seen from the above table, product of the invention can be applied to 3D printing notebook computer casing In, and during the product of prior art may not apply to 3D printing notebook computer casing.
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 preparation technology of the modified 3D printing material of a kind of Graphene, it is characterised in that comprise the following steps：
S1：200-300 mesh sieve is crossed after ABS resin 86-124 parts is crushed with zinc acrylate resin 24-38 parts, compound tree is obtained Cosmetics end；
S2：It is 68-72 DEG C, rotating speed in temperature to 1-1.6 parts of surfactant is added in hybrid resin powder obtained in step S1 To activate 1-1.3h under 150-180r/min, activation hybrid resin powder is obtained；
S3：By Graphene 1.8-4.2 parts of crushing, 200-300 mesh sieve is crossed, powder is obtained, gained powder is in magnetic field intensity 7000-8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 40- 50min, is obtained Graphene energy powder；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation hybrid resin powder obtained in step S2 Amount powder, PLA 54-76 parts, two polyphosphate sodium 46-62 parts, 12-16 parts of chloropropyl styrene, maleic anhydride inoculated polypropylene 10-14 parts, sodium cellulose glycolate 8-12 parts, Kafra fiber 4-6 parts, 3-5 parts of polybutylene terephthalate (PBT) fiber, adjust Section 0.4-0.8 parts of agent, propellant 0.3-0.5 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.7-1.3 parts, bridging agent 0.5-1 parts, Catalyst 0.3-0.5 parts, plasticizer 0.5-0.8 parts, dispersant 0.3-0.5 parts, tackifier 0.4-0.7 parts, it is in microwave power 300-350W, temperature is 138-145 DEG C, and rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To 1-2.3 parts of curing agent of addition, antioxidant 0.3-0.5 parts, stabilizer 0.2-0.4 in mixture I obtained in step S4 Part, antiager 1.2-1.8 part, fire retardant 1.8-2.4 part, temperature be 76-80 DEG C, rotating speed be 150-250r/min under stirring 1.6-2h, is obtained mixture II；
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 3D printing material of Graphene is obtained.
2. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that in step S2 The surfactant is Pluronic F68.
3. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that in step S4 The conditioning agent is ACR, and the propellant is aerogel generating agent.
4. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that in step S4 The crosslinking agent is crosslinking aid S AC-100, and the compatilizer is that maleic anhydride is grafted compatilizer.
5. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that the bridge formation Agent is acrylic type bridging agent, and the catalyst is vanadic anhydride.
6. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that in step S4 The plasticizer is citrate, and the dispersant is Dispersant MF, and the tackifier are butyl trimethoxy silane.
7. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that step S, 5 Described in curing agent be epoxylite curing agent.
8. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that step S, 5 Described in antioxidant be antioxidant 2246, the stabilizer be modified alta-mud heat stabilizer.
9. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that step S, 5 Described in antiager be BASF UV-234 antiagers.
10. the preparation technology of the modified 3D printing material of Graphene according to claim 1, it is characterised in that step S, 5 Described in fire retardant in units of weight portion, including following raw material：Ethylene glycol ether acetate 60-68 parts, Caprylic Capric 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.
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Application publication date: 20170613