CN106496983A - A kind of graphene composite material of 3D printing - Google Patents
A kind of graphene composite material of 3D printing Download PDFInfo
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- CN106496983A CN106496983A CN201611012960.5A CN201611012960A CN106496983A CN 106496983 A CN106496983 A CN 106496983A CN 201611012960 A CN201611012960 A CN 201611012960A CN 106496983 A CN106496983 A CN 106496983A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses a kind of graphene composite material of 3D printing, belongs to 3D printing technical field of material, the graphene composite material of the 3D printing in units of weight portion, including following raw material：4.8 7.6 parts of Graphene, 23.9 30.4 parts of waste plastic, 32.8 38.2 parts of polylactic acid, 12.4 22.7 parts of two PA 800K, 17.6 24.5 parts of acrylate, 8.9 17.3 parts of specific syntheticses, 4.7 9.5 parts of Starch synthesis agent.The graphene composite material of the 3D printing that the present invention makes has tensile strength, bending strength and notch impact strength big, the features such as heat distortion temperature and high melt index, the product high-quality that printed by 3D printing technique, high-impact, high intensity, with wide market prospect.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of Graphene composite wood of 3D printing
Material.
【Background technology】
One kind of 3D printing, i.e. rapid shaping technique, it are a kind of based on mathematical model file, with powdered gold
Category or plastics etc. can jointing material, come the technology of constructed object by way of successively printing.3D printing is typically with numeral
Technologic material printer is often used for modeling in fields such as Making mold, industrial designs realized, after be gradually available for one
The direct manufacture of a little products, has had the parts printed using this technology, the technology to set in jewelry, footwear, industry
Meter, building, engineering and construction (AEC), automobile, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System, building work
Journey, gun and other field have all been applied.Although 3D printing technique has above-mentioned technical advantage, from other side
For, there is certain inferior position again, in terms of emphasis is embodied in material, it may be said that be a very big short slab, material function
Industry development is not caught up with, large forgings cannot be embarked on journey, the factors such as poor mechanical property directly govern overall development.With
The increase of 3D printing market demand, 3D printing material function do not catch up with industry development, how to break through raising 3D printing material
Feature, reduction 3D printing cost, improve situations such as mechanical property of 3D printing material, solution resource recycling and have compeled
In the eyebrows and eyelashes.
Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made up of carbon atom
Two dimensional crystal.Graphene is both most thin material, and most tough material, and fracture strength is more taller than best steel
200 times.It has good elasticity, stretch range reach the 20% of own dimensions again simultaneously.It is that current nature is most thin, strong
Degree highest material, if making hammock with the Graphene of 1 square metre of one piece of area, weight itself just can be held less than 1 milligram
By one one kilogram of cat.
As the most strong a kind of novel nano-material of the most thin, maximum intensity, electrical and thermal conductivity performance that have now been found that, Graphene
It is referred to as " dark fund ", is " king of new material ", scientist even foretells that Graphene " will thoroughly change 21 century ".Very likely lift
Play a subversiveness new technique new industrial revolution that have swepts the globe.
Current plastics 3d printing materials little, the thermal deformation temperature that there is tensile strength, bending strength and notch impact strength
Degree and the low problem of melt index, therefore, research and development are a kind of to have high intensity, and heat conductivity is good, while having with high tenacity and melting
The graphene composite material for melting the 3D printing of index has great importance.
【Content of the invention】
The present invention provides a kind of graphene composite material of 3D printing, exists with material to solve existing plastics 3d printings
Tensile strength, bending strength and notch impact strength little, heat distortion temperature and the low problem of melt index.The present invention makes
The graphene composite material of 3D printing has tensile strength, bending strength and notch impact strength big, heat distortion temperature and molten
Melt index high the features such as, the product high-quality that printed by 3D printing technique, high-impact, high intensity, with wide city
Field prospect.
For solving above technical problem, the present invention is employed the following technical solutions：
A kind of graphene composite material of 3D printing, in units of weight portion, including following raw material：Graphene 4.8-
7.6 parts, waste plastic 23.9-30.4 parts, polylactic acid 32.8-38.2 parts, two PA 800K 12.4-22.7 parts, acrylate
17.6-24.5 parts, specific syntheticses 8.9-17.3 parts, Starch synthesis agent 4.7-9.5 parts；
The specific syntheticses in units of weight portion, including following raw material：Regulator 15-22 parts, propellant 12-18
Part, coupling agent a 10-15 parts, compatilizer 12-16 parts, plasticizer a 9-12 parts, antioxidant 6-10 parts, flocculation agent 5-9 parts, end
Only agent 3-5 parts, stabilizer a 2-4 parts；
The Starch synthesis agent in units of weight portion, including following raw material：Starch 80-130 parts, Glutaric Acid Dimethyl ester
10-16 parts, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 1.5-3.5 parts, paste agent 1-2 parts, coupling
Agent b 0.2-0.6 parts, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer b 0.1-0.3 parts, defoamer 0.3-0.8
Part, plasticizer b 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial
0.1-0.2 parts；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer b is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, followed by batch type plastic cleaning
The waste plastic of broken mistake is carried out thoroughly cleaning by machine, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90-- in temperature
By plastic crushing 2-3h at 110 DEG C, the plastic grains of 400-600 mesh after sieving, are obtained；
S4：Polylactic acid, dimerization are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, acrylate, specific syntheticses, are warming up to 202-218 DEG C, are that stirring melts 2.1- under 200-400r/min in rotating speed
3.2h, is subsequently cooled to room temperature, and modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S42：To in material A obtained in step S41, add regulator, flocculation agent 143-156 DEG C to be warming up to after mixing, turning
Speed is obtained material B for reacting 145-232min under 300-400r/min；
S43：To in material B obtained in step S42, add plasticizer a, terminator, stabilizer a to be cooled to 108- after mixing
125 DEG C, be 62-135min to be reacted under 200-300r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -90--110 DEG C,
Starch synthesis agent mix homogeneously is added, mix homogeneously mixture is put in screw extruding forming machine, be 180-200 in temperature
DEG C, rotating speed is under 110-130r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', starch slurry a of the pH value for 3.1-3.8；
S52：Concentration is added in starch slurry a obtained in step S51 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- diformazans
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is to carry out crosslinking and connect under 70-100r/min
Branch reaction 2.5-3.5h, is obtained slurry b；
S53：Paste agent is added in slurry b obtained in step S52, and regulation pH value is 9.1-9.8, is subsequently added into epoxy chlorine
Butane, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, then temperature be 55-61 DEG C, stirring
Rotating speed is to carry out cross-linking reaction 1.2-1.8h under 80-120r/min, and slurry c is obtained；
S54：Stabilizer b will be added in slurry c obtained in step S53, regulation pH value is 8.3-8.5, is warming up to 73-77
DEG C, gelatinizing 50-55min, gelatinizing are down to 30-33 DEG C after terminating, add defoamer, are to stir 8- under 90-130r/min in rotating speed
12min, is obtained Starch synthesis agent.
Further, the regulator is ACR.
Further, the propellant is aerogel generating agent.
Further, the coupling agent a is Silane coupling agent KH550.
Further, the compatilizer is that maleic anhydride is grafted compatilizer.
Further, the plasticizer a is dicyclohexyl phthalate.
Further, the antioxidant is Ronotec17.
Further, the flocculation agent is aluminium polychlorid.
Further, the terminator is wood tar.
Further, the stabilizer a is rare-earth stabilizer.
The invention has the advantages that：
(1) present invention uses waste plastic, and source is wide, and price is low, has widened the range of choice of 3D printing material feedstock；
(2) graphene composite material of the 3D printing that the present invention makes has the punching of tensile strength, bending strength and breach
Hit intensity is big, the features such as heat distortion temperature and high melt index, the product high-quality that printed by 3D printing technique, high anti-
Punching, high intensity, with wide market prospect；
(3) the graphene composite material low cost of the 3D printing that the present invention makes, it is easy to industrialized production.
【Specific embodiment】
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to the present invention's
Protection domain, but do not limit the scope of the invention.
In an embodiment, the graphene composite material of the 3D printing, in units of weight portion, including following raw material：
Graphene 4.8-7.6 parts, waste plastic 23.9-30.4 parts, polylactic acid 32.8-38.2 parts, two PA 800K 12.4-22.7 parts,
Acrylate 17.6-24.5 parts, specific syntheticses 8.9-17.3 parts, Starch synthesis agent 4.7-9.5 parts；
The specific syntheticses in units of weight portion, including following raw material：Regulator 15-22 parts, propellant 12-18
Part, coupling agent a 10-15 parts, compatilizer 12-16 parts, plasticizer 9-12 parts, antioxidant 6-10 parts, flocculation agent 5-9 parts, termination
Agent 3-5 parts, stabilizer a 2-4 parts；
The regulator is ACR；
The propellant is aerogel generating agent；
The coupling agent a is Silane coupling agent KH550；
The compatilizer is that maleic anhydride is grafted compatilizer；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The antioxidant is Ronotec17；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer a is rare-earth stabilizer；
The Starch synthesis agent in units of weight portion, including following raw material：Starch 80-130 parts, Glutaric Acid Dimethyl ester
10-16 parts, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 1.5-3.5 parts, paste agent 1-2 parts, coupling
Agent b 0.2-0.6 parts, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer b 0.1-0.3 parts, defoamer 0.3-0.8
Part, plasticizer 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial 0.1-
0.2 part；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, followed by batch type plastic cleaning
The waste plastic of broken mistake is carried out thoroughly cleaning by machine, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90-- in temperature
By plastic crushing 2-3h at 110 DEG C, the plastic grains of 400-600 mesh after sieving, are obtained；
S4：Polylactic acid, dimerization are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, acrylate, specific syntheticses, are warming up to 202-218 DEG C, are that stirring melts 2.1- under 200-400r/min in rotating speed
3.2h, is subsequently cooled to room temperature, and modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S42：To in material A obtained in step S41, add regulator, flocculation agent 143-156 DEG C to be warming up to after mixing, turning
Speed is obtained material B for reacting 145-232min under 300-400r/min；
S43：To in material B obtained in step S42, add plasticizer, terminator, stabilizer a to be cooled to 108- after mixing
125 DEG C, be 62-135min to be reacted under 200-300r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -90--110 DEG C,
Starch synthesis agent mix homogeneously is added, mix homogeneously mixture is put in screw extruding forming machine, be 180-200 in temperature
DEG C, rotating speed is under 110-130r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', starch slurry a of the pH value for 3.1-3.8；
S52：Concentration is added in starch slurry a obtained in step S51 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- diformazans
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is to carry out crosslinking and connect under 70-100r/min
Branch reaction 2.5-3.5h, is obtained slurry b；
S53：Paste agent is added in slurry b obtained in step S52, and regulation pH value is 9.1-9.8, is subsequently added into epoxy chlorine
Butane, carbamide, initiator, plasticizer, toughener, viscosifier, water-proofing agent, antibacterial, then temperature be 55-61 DEG C, stirring
Rotating speed is to carry out cross-linking reaction 1.2-1.8h under 80-120r/min, and slurry c is obtained；
S54：Stabilizer b will be added in slurry c obtained in step S53, regulation pH value is 8.3-8.5, is warming up to 73-77
DEG C, gelatinizing 50-55min, gelatinizing are down to 30-33 DEG C after terminating, add defoamer, are to stir 8- under 90-130r/min in rotating speed
12min, is obtained Starch synthesis agent.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of graphene composite material of the 3D printing, in units of weight portion, including following raw material：Graphene
6.6 parts, 28 parts of waste plastic, 38 parts of polylactic acid, 20 parts of two PA 800K, 24 parts of acrylate, 16 parts of specific syntheticses, starch
8 parts of syntheticses；
The specific syntheticses in units of weight portion, including following raw material：18 parts of regulator, 15 parts of propellant, coupling
13 parts of agent a, 14 parts of compatilizer, 10 parts of plasticizer, 8 parts of antioxidant, 7 parts of flocculation agent, 4 parts of terminator, 3 parts of stabilizer a；
The regulator is ACR；
The propellant is aerogel generating agent；
The coupling agent a is Silane coupling agent KH550；
The compatilizer is that maleic anhydride is grafted compatilizer；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The antioxidant is Ronotec17；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer a is rare-earth stabilizer；
The Starch synthesis agent in units of weight portion, including following raw material：116 parts of starch, 13 parts of Glutaric Acid Dimethyl ester,
11 parts of N,N-dimethylacetamide, 4 parts of epoxy chlorobutane, 2.5 parts of carbamide, 1.5 parts of paste agent, 0.4 part of coupling agent b, initiator
0.1 part, 0.1 part of catalyst, 0.2 part of stabilizer b, 0.6 part of defoamer, 0.7 part of plasticizer, 0.5 part of toughener, viscosifier 0.4
Part, 0.3 part of water-proofing agent, 0.1 part of antibacterial；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, followed by batch type plastic cleaning
The waste plastic of broken mistake is carried out thoroughly cleaning by machine, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -100 DEG C in temperature
Lower by plastic crushing 2.5h, obtain the plastic grains of 500 mesh after sieving；
S4：Polylactic acid, dimerization are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, acrylate, specific syntheticses, are warming up to 210 DEG C, are that stirring melts 2.6h, Ran Houleng under 300r/min in rotating speed
But to room temperature, modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 122 DEG C, are 150r/min in rotating speed
Lower reaction 75min, is obtained material A；
S42：To in material A obtained in step S41, add regulator, flocculation agent 150 DEG C to be warming up to after mixing, in rotating speed be
190min is reacted under 350r/min, material B is obtained；
S43：To in material B obtained in step S42, add plasticizer, terminator, stabilizer a to be cooled to 116 DEG C after mixing,
Be 100min to be reacted under 250r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -100 DEG C, is added
Starch synthesis agent mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 190 DEG C in temperature, and rotating speed is
Under 120r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 22Be ', and pH value is 3.5 starch slurry a；
S52：Glutaric Acid Dimethyl ester, N that concentration is 6%, N- dimethyl second is added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, then temperature be 50 DEG C, speed of agitator be 90r/min under carry out cross-linked graft reaction 3h, system
Obtain slurry b；
S53：Paste agent is added in slurry b obtained in step S52, it is 9.5 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer, toughener, viscosifier, water-proofing agent, antibacterial, are then 58 DEG C in temperature, and speed of agitator is
Cross-linking reaction 1.5h is carried out under 100r/min, slurry c is obtained；
S54：Stabilizer b will be added in slurry c obtained in step S53, it is 8.4 to adjust pH value, is warming up to 75 DEG C, gelatinizing
53min, gelatinizing are down to 32 DEG C after terminating, add defoamer, be to stir 10min under 120r/min in rotating speed, Starch synthesis are obtained
Agent.
Embodiment 2
A kind of graphene composite material of the 3D printing, in units of weight portion, including following raw material：Graphene
4.8 parts, 23.9 parts of waste plastic, 32.8 parts of polylactic acid, 12.4 parts of two PA 800K, 17.6 parts of acrylate, specific syntheticses
8.9 parts, 4.7 parts of Starch synthesis agent；
The specific syntheticses in units of weight portion, including following raw material：15 parts of regulator, 12 parts of propellant, coupling
10 parts of agent a, 12 parts of compatilizer, 9 parts of plasticizer, 6 parts of antioxidant, 5 parts of flocculation agent, 3 parts of terminator, 2 parts of stabilizer a；
The regulator is ACR；
The propellant is aerogel generating agent；
The coupling agent a is Silane coupling agent KH550；
The compatilizer is that maleic anhydride is grafted compatilizer；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The antioxidant is Ronotec17；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer a is rare-earth stabilizer；
The Starch synthesis agent in units of weight portion, including following raw material：80 parts of starch, 10 parts of Glutaric Acid Dimethyl ester,
8 parts of N,N-dimethylacetamide, 2 parts of epoxy chlorobutane, 1.5 parts of carbamide, 1 part of paste agent, 0.2 part of coupling agent b, initiator 0.1
Part, 0.1 part of catalyst, 0.1 part of stabilizer b, 0.3 part of defoamer, 0.4 part of plasticizer, 0.3 part of toughener, 0.3 part of viscosifier,
0.2 part of water-proofing agent, 0.1 part of antibacterial；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, followed by batch type plastic cleaning
The waste plastic of broken mistake is carried out thoroughly cleaning by machine, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are at -90 DEG C in temperature
By plastic crushing 3h, the plastic grains of 400 mesh after sieving, are obtained；
S4：Polylactic acid, dimerization are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, acrylate, specific syntheticses, are warming up to 202 DEG C, are that stirring melts 3.2h, Ran Houleng under 200r/min in rotating speed
But to room temperature, modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 117 DEG C, are 100r/min in rotating speed
Lower reaction 82min, is obtained material A；
S42：To in material A obtained in step S41, add regulator, flocculation agent 143 DEG C to be warming up to after mixing, in rotating speed be
145min is reacted under 300r/min, material B is obtained；
S43：To in material B obtained in step S42, add plasticizer, terminator, stabilizer a to be cooled to 108 DEG C after mixing,
Be 135min to be reacted under 200r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -90 DEG C, is added and is formed sediment
Powder syntheticses mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 180 DEG C in temperature, and rotating speed is
Under 110r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18Be ', and pH value is 3.1 starch slurry a；
S52：Glutaric Acid Dimethyl ester, N that concentration is 4%, N- dimethyl second is added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, then temperature be 42 DEG C, speed of agitator be 70r/min under carry out cross-linked graft reaction 2.5h,
Prepared slurry b；
S53：Paste agent is added in slurry b obtained in step S52, it is 9.1 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer, toughener, viscosifier, water-proofing agent, antibacterial, are then 55 DEG C in temperature, and speed of agitator is
Cross-linking reaction 1.8h is carried out under 80r/min, slurry c is obtained；
S54：Stabilizer b will be added in slurry c obtained in step S53, it is 8.3 to adjust pH value, is warming up to 73 DEG C, gelatinizing
55min, gelatinizing are down to 30 DEG C after terminating, add defoamer, be to stir 12min under 90r/min in rotating speed, Starch synthesis are obtained
Agent.
Embodiment 3
A kind of graphene composite material of the 3D printing, in units of weight portion, including following raw material：Graphene
7.6 parts, 30.4 parts of waste plastic, 38.2 parts of polylactic acid, 22.7 parts of two PA 800K, 24.5 parts of acrylate, specific syntheticses
17.3 parts, 9.5 parts of Starch synthesis agent；
The specific syntheticses in units of weight portion, including following raw material：22 parts of regulator, 18 parts of propellant, coupling
15 parts of agent a, 16 parts of compatilizer, 12 parts of plasticizer, 10 parts of antioxidant, 9 parts of flocculation agent, 5 parts of terminator, 4 parts of stabilizer a；
The regulator is ACR；
The propellant is aerogel generating agent；
The coupling agent a is Silane coupling agent KH550；
The compatilizer is that maleic anhydride is grafted compatilizer；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The antioxidant is Ronotec17；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer a is rare-earth stabilizer；
The Starch synthesis agent in units of weight portion, including following raw material：130 parts of starch, 16 parts of Glutaric Acid Dimethyl ester,
13 parts of N,N-dimethylacetamide, 5 parts of epoxy chlorobutane, 3.5 parts of carbamide, 2 parts of paste agent, 0.6 part of coupling agent b, initiator
0.2 part, 0.2 part of catalyst, 0.3 part of stabilizer b, 0.8 part of defoamer, 0.9 part of plasticizer, 0.7 part of toughener, viscosifier 0.6
Part, 0.4 part of water-proofing agent, 0.2 part of antibacterial；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, followed by batch type plastic cleaning
The waste plastic of broken mistake is carried out thoroughly cleaning by machine, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -110 DEG C in temperature
Lower by plastic crushing 2h, obtain the plastic grains of 600 mesh after sieving；
S4：Polylactic acid, dimerization are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, acrylate, specific syntheticses, are warming up to 218 DEG C, are that stirring melts 2.1h, Ran Houleng under 400r/min in rotating speed
But to room temperature, modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 128 DEG C, are 200r/min in rotating speed
Lower reaction 68min, is obtained material A；
S42：To in material A obtained in step S41, add regulator, flocculation agent 156 DEG C to be warming up to after mixing, in rotating speed be
145min is reacted under 400r/min, material B is obtained；
S43：To in material B obtained in step S42, add plasticizer, terminator, stabilizer a to be cooled to 125 DEG C after mixing,
Be 62min to be reacted under 300r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -110 DEG C, is added
Starch synthesis agent mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 200 DEG C in temperature, and rotating speed is
Under 130r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 25Be ', and pH value is 3.8 starch slurry a；
S52：Glutaric Acid Dimethyl ester, N that concentration is 8%, N- dimethyl second is added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, then temperature be 58 DEG C, speed of agitator be 100r/min under carry out cross-linked graft reaction
2.5h, is obtained slurry b；
S53：Paste agent is added in slurry b obtained in step S52, it is 9.8 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer, toughener, viscosifier, water-proofing agent, antibacterial, are then 61 DEG C in temperature, and speed of agitator is
Cross-linking reaction 1.2h is carried out under 120r/min, slurry c is obtained；
S54：Stabilizer b will be added in slurry c obtained in step S53, it is 8.5 to adjust pH value, is warming up to 77 DEG C, gelatinizing
50min, gelatinizing are down to 33 DEG C after terminating, add defoamer, be to stir 8min under 130r/min in rotating speed, Starch synthesis are obtained
Agent.
3D printing in embodiment 1-3 with graphene composite material performance detect, as a result as shown in the table.
As seen from the above table, the graphene composite material of 3D printing of the invention has tensile strength, bending strength and lacks
Mouthful impact strength is big, the features such as heat distortion temperature and high melt index, the product high-quality that printed by 3D printing technique,
High-impact, high intensity.
Above content it cannot be assumed that the present invention is embodied as being confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of without departing from present inventive concept, some simple deduction or replace can also be made, all answered
When being considered as belonging to the scope of patent protection that determined by the claims that is submitted to of the present invention.
Claims (10)
1. a kind of graphene composite material of 3D printing, it is characterised in that in units of weight portion, including following raw material：Stone
Black alkene 4.8-7.6 parts, waste plastic 23.9-30.4 parts, polylactic acid 32.8-38.2 parts, two PA 800K 12.4-22.7 parts, third
Olefin(e) acid ester 17.6-24.5 parts, specific syntheticses 8.9-17.3 parts, Starch synthesis agent 4.7-9.5 parts；
The specific syntheticses in units of weight portion, including following raw material：Regulator 15-22 parts, propellant 12-18 parts, idol
Connection agent a 10-15 parts, compatilizer 12-16 parts, plasticizer a 9-12 parts, antioxidant 6-10 parts, flocculation agent 5-9 parts, terminator
3-5 parts, stabilizer a 2-4 parts；
The Starch synthesis agent in units of weight portion, including following raw material：Starch 80-130 parts, Glutaric Acid Dimethyl ester 10-16
Part, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 1.5-3.5 parts, paste agent 1-2 parts, coupling agent b
0.2-0.6 parts, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer b 0.1-0.3 parts, defoamer 0.3-0.8 parts,
Plasticizer b 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial 0.1-
0.2 part；
The coupling agent b is titanate coupling agent；
The initiator is two isopropylformic acid. of azo (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer b is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether；
The plasticizer b is phthalic acid two (2- ethyl hexyls) ester；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the graphene composite material of described 3D printing, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, and primary graphene powder is obtained through special handling；
S2：Preliminary crushing is carried out to waste plastic using duroplastss disintegrating machine, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90--110 DEG C in temperature
Lower by plastic crushing 2-3h, obtain the plastic grains of 400-600 mesh after sieving；
S4：Polylactic acid, two polyphosphoric acids are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium, acrylate, specific syntheticses, are warming up to 202-218 DEG C, are that stirring melts 2.1- under 200-400r/min in rotating speed
3.2h, is subsequently cooled to room temperature, and modified Graphene 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S41：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to 117-128 DEG C, are 100-200r/ in rotating speed
68-82min is reacted under min, material A is obtained；
S42：To in material A obtained in step S41, add regulator, flocculation agent 143-156 DEG C to be warming up to after mixing, in rotating speed be
145-232min is reacted under 300-400r/min, material B is obtained；
S43：To in material B obtained in step S42, add plasticizer a, terminator, stabilizer a to be cooled to 108-125 after mixing
DEG C, be 62-135min to be reacted under 200-300r/min in rotating speed, specific syntheticses are obtained；
S5：Modified Graphene 3D printing secondary-material obtained in step S4 is crushed in the case where temperature is for -90--110 DEG C, is added
Starch synthesis agent mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 180-200 DEG C in temperature, is turned
Speed is under 110-130r/min, through extruding strand, the graphene composite material of prepared 3D printing；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', starch slurry a of the pH value for 3.1-3.8；
S52：Concentration is added in starch slurry a obtained in step S51 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- dimethyl second
Amide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is that under 70-100r/min to carry out cross-linked graft anti-
2.5-3.5h is answered, slurry b is obtained；
S53：Paste agent is added in slurry b obtained in step S52, and regulation pH value is 9.1-9.8, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, then temperature be 55-61 DEG C, stirring turn
Speed is obtained slurry c for carrying out cross-linking reaction 1.2-1.8h under 80-120r/min；
S54：Stabilizer b will be added in slurry c obtained in step S53, regulation pH value is 8.3-8.5, is warming up to 73-77 DEG C, pastes
Change 50-55min, gelatinizing is down to 30-33 DEG C after terminating, add defoamer, be 8-12min to be stirred under 90-130r/min in rotating speed,
Prepared Starch synthesis agent.
2. the graphene composite material of 3D printing according to claim 1, it is characterised in that the regulator is
ACR.
3. the graphene composite material of 3D printing according to claim 1, it is characterised in that the propellant is aerosol
Propellant.
4. the graphene composite material of 3D printing according to claim 1, it is characterised in that the coupling agent a is silane
Coupling agent KH550.
5. the graphene composite material of 3D printing according to claim 1, it is characterised in that the compatilizer is maleic acid
Acid anhydride is grafted compatilizer.
6. the graphene composite material of 3D printing according to claim 1, it is characterised in that the plasticizer a is adjacent benzene
Dioctyl phthalate dicyclohexyl maleate.
7. the graphene composite material of 3D printing according to claim 1, it is characterised in that the antioxidant is
Ronotec17.
8. the graphene composite material of 3D printing according to claim 1, it is characterised in that the flocculation agent is polymerization chlorine
Change aluminum.
9. the graphene composite material of 3D printing according to claim 1, it is characterised in that the terminator is burnt for wood
Oil.
10. the graphene composite material of 3D printing according to claim 1, it is characterised in that the stabilizer a is rare earth
Stabilizer.
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