CN106633717A - Graphene 3D (three-dimensional) print material with high impact strength - Google Patents
Graphene 3D (three-dimensional) print material with high impact strength Download PDFInfo
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- CN106633717A CN106633717A CN201611012965.8A CN201611012965A CN106633717A CN 106633717 A CN106633717 A CN 106633717A CN 201611012965 A CN201611012965 A CN 201611012965A CN 106633717 A CN106633717 A CN 106633717A
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- 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
- 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
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- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a graphene 3D (three-dimensional) print material with high impact strength and belongs to the technical field of materials for 3D printing. The graphene 3D print material with high impact strength comprises the following raw materials in parts by weight: 5.5-7.7 parts of graphene, 24.6-31 parts of waste plastics, 34.2-40 parts of polylactic acid, 11.6-23 parts of potassium hexaphosphate, 18.3-24 parts of epoxy acrylate, 9.2-18 parts of a specific synthetic agent and 5.2-9 parts of a starch synthetic agent. The graphene 3D print material prepared in the invention has the characteristics of high tensile strength, bending strength and notch impact strength, high thermal deformation temperature, high melt index and the like, and the product printed by a 3D printing technology is high in quality, impact resistance and strength and has wide market prospects.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of Graphene with high impact strength
3D printing material.
【Background technology】
One kind of 3D printing, i.e. rapid shaping technique, it is 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 come what is realized in fields such as Making mold, industrial designs, after be gradually available for one
The direct manufacture of a little products, has there is the parts printed using this technology, and the technology sets 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, emphasis is embodied in material aspect, it may be said that be a very big short slab, material function
Industry development is not caught up with, large forgings cannot embark 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, is also most tough material, and fracture strength is more taller than best steel
200 times.Simultaneously it has good elasticity again, and stretch range can reach the 20% of own dimensions.It is that current nature is most thin, strong
Degree highest material, if making hammock with the Graphene of one piece of 1 square metre of area, weight itself just can hold 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 have swept 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 3D printing material for melting index has great importance.
【The content of the invention】
The present invention provides a kind of Graphene 3D printing material with high impact strength, and to solve existing plastics 3d use is printed
It is little that material has tensile strength, bending strength and a notch impact strength, heat distortion temperature and the low problem of melt index.This
Graphene 3D printing material made by bright has tensile strength, bending strength and notch impact strength big, heat distortion temperature and molten
Melt index it is high the features such as, product high-quality, high-impact, the high intensity printed by 3D printing technique, with wide city
Field prospect.
To solve above technical problem, the present invention is employed the following technical solutions：
A kind of Graphene 3D printing material with high impact strength, in units of weight portion, including following raw material：Graphite
Alkene 5.5-7.7 parts, waste plastic 24.6-31 parts, polylactic acid 34.2-40 parts, six PA 800K 11.6-23 parts, epoxy acrylic
Ester 18.3-24 parts, specific syntheticses 9.2-18 parts, Starch synthesis agent 5.2-9 parts；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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 are obtained after sieving；
S4：Polylactic acid, six are added to gather in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, epoxy acrylate, specific syntheticses, are warming up to 194-220 DEG C, and the stirring in the case where rotating speed is 200-400r/min melts
2.2-3.4h, 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 into 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S42：Add in material A obtained in step S41 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S43：Add in material B obtained in step S42 and be cooled to 108- after plasticizer a, terminator, stabilizer a mixing
125 DEG C, 62-135min is reacted in the case where rotating speed is 200-300r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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 Jing extruding strands under 110-130r/min, and the Graphene 3D printing material with high impact strength is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 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 under 70-100r/min to connect
Branch reaction 2.5-3.5h, is obtained slurry b；
S53：Paste agent is added in slurry b obtained in step S52, 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, are then 55-61 DEG C in temperature, 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 is down to 30-33 DEG C after terminating, add defoamer, and in the case where rotating speed is 90-130r/min 8- is stirred
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 3D printing material made by the present invention has tensile strength, bending strength and notch impact strength big,
It is the features such as heat distortion temperature and high melt index, the product high-quality printed by 3D printing technique, high-impact, high-strength
Degree, with wide market prospect；
(3) the cost of material is low for the Graphene 3D printing with high impact strength made by the present invention, 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 embodiment, the Graphene 3D printing material with high impact strength, in units of weight portion, including with
Lower raw material：Graphene 5.5-7.7 parts, waste plastic 24.6-31 parts, polylactic acid 34.2-40 parts, six PA 800K 11.6-23 parts,
Epoxy acrylate 18.3-24 parts, specific syntheticses 9.2-18 parts, Starch synthesis agent 5.2-9 parts；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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 are obtained after sieving；
S4：Polylactic acid, six are added to gather in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, epoxy acrylate, specific syntheticses, are warming up to 194-220 DEG C, and the stirring in the case where rotating speed is 200-400r/min melts
2.2-3.4h, 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 into 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S42：Add in material A obtained in step S41 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S43：Add in material B obtained in step S42 and be cooled to 108- after plasticizer, terminator, stabilizer a mixing
125 DEG C, 62-135min is reacted in the case where rotating speed is 200-300r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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 Jing extruding strands under 110-130r/min, and the Graphene 3D printing material with high impact strength is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 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 under 70-100r/min to connect
Branch reaction 2.5-3.5h, is obtained slurry b；
S53：Paste agent is added in slurry b obtained in step S52, regulation pH value is 9.1-9.8, is subsequently added into epoxy chlorine
Butane, carbamide, initiator, plasticizer, toughener, viscosifier, water-proofing agent, antibacterial, are then 55-61 DEG C in temperature, 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 is down to 30-33 DEG C after terminating, add defoamer, and in the case where rotating speed is 90-130r/min 8- is stirred
12min, is obtained Starch synthesis agent.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of Graphene 3D printing material with high impact strength, in units of weight portion, including following raw material：
6.6 parts of Graphene, 28 parts of waste plastic, 38 parts of polylactic acid, 20 parts of six PA 800K, 24 parts of epoxy acrylate, specific synthesis
16 parts of agent, 8 parts of Starch synthesis agent；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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
It is lower by plastic crushing 2.5h, the plastic grains of 500 mesh are obtained after sieving；
S4：Polylactic acid, six are added to gather in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, epoxy acrylate, specific syntheticses, are warming up to 212 DEG C, and the stirring in the case where rotating speed is 300r/min melts 2.8h, so
After be cooled 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 into 122 DEG C, are 150r/min in rotating speed
Lower reaction 75min, is obtained material A；
S42：Add in material A obtained in step S41 and be warming up to 150 DEG C after regulator, flocculation agent mixing, be in rotating speed
190min is reacted under 350r/min, material B is obtained；
S43：Add in material B obtained in step S42 and be cooled to 116 DEG C after plasticizer, terminator, stabilizer a mixing,
100min is reacted in the case where rotating speed is 250r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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, Jing extruding strands are obtained the Graphene 3D printing material with high impact strength；
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 are added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, are then 50 DEG C in temperature, and speed of agitator is that cross-linked graft reaction 3h, system are carried out under 90r/min
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 is down to 32 DEG C after terminating, add defoamer, and in the case where rotating speed is 120r/min 10min is stirred, and Starch synthesis are obtained
Agent.
Embodiment 2
A kind of Graphene 3D printing material with high impact strength, in units of weight portion, including following raw material：
5.5 parts of Graphene, 24.6 parts of waste plastic, 34.2 parts of polylactic acid, 11.6 parts of six PA 800K, 18.3 parts of epoxy acrylate,
9.2 parts of specific syntheticses, 5.2 parts of Starch synthesis agent；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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, in the case where temperature is for -90 DEG C
By plastic crushing 3h, the plastic grains of 400 mesh are obtained after sieving；
S4：Polylactic acid, six are added to gather in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, epoxy acrylate, specific syntheticses, are warming up to 194 DEG C, and the stirring in the case where rotating speed is 200r/min melts 3.4h, so
After be cooled 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 into 117 DEG C, are 100r/min in rotating speed
Lower reaction 82min, is obtained material A；
S42：Add in material A obtained in step S41 and be warming up to 143 DEG C after regulator, flocculation agent mixing, be in rotating speed
145min is reacted under 300r/min, material B is obtained；
S43：Add in material B obtained in step S42 and be cooled to 108 DEG C after plasticizer, terminator, stabilizer a mixing,
135min is reacted in the case where rotating speed is 200r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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, Jing extruding strands are obtained the Graphene 3D printing material with high impact strength；
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 are added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, are then 42 DEG C in temperature, and speed of agitator is that cross-linked graft reaction 2.5h is carried out under 70r/min,
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 is down to 30 DEG C after terminating, add defoamer, and in the case where rotating speed is 90r/min 12min is stirred, and Starch synthesis are obtained
Agent.
Embodiment 3
A kind of Graphene 3D printing material with high impact strength, in units of weight portion, including following raw material：
7.7 parts of Graphene, 31 parts of waste plastic, 40 parts of polylactic acid, 23 parts of six PA 800K, 24 parts of epoxy acrylate, specific synthesis
18 parts of agent, 9 parts of Starch synthesis agent；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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
It is lower by plastic crushing 2h, the plastic grains of 600 mesh are obtained after sieving；
S4：Polylactic acid, six are added to gather in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium phosphate, epoxy acrylate, specific syntheticses, are warming up to 220 DEG C, and the stirring in the case where rotating speed is 400r/min melts 2.2h, so
After be cooled 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 into 128 DEG C, are 200r/min in rotating speed
Lower reaction 68min, is obtained material A；
S42：Add in material A obtained in step S41 and be warming up to 156 DEG C after regulator, flocculation agent mixing, be in rotating speed
145min is reacted under 400r/min, material B is obtained；
S43：Add in material B obtained in step S42 and be cooled to 125 DEG C after plasticizer, terminator, stabilizer a mixing,
62min is reacted in the case where rotating speed is 300r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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, Jing extruding strands are obtained the Graphene 3D printing material with high impact strength；
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 are added in starch slurry a obtained in step S51
Amide, coupling agent b, catalyst, are then 58 DEG C in temperature, and speed of agitator is to carry out cross-linked graft reaction under 100r/min
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 is down to 33 DEG C after terminating, add defoamer, and in the case where rotating speed is 130r/min 8min is stirred, and Starch synthesis are obtained
Agent.
The Graphene 3D printing material property with high impact strength in embodiment 1-3 is detected, as a result as follows
Shown in table.
As seen from the above table, Graphene 3D printing material of the invention has tensile strength, bending strength and notch shock strong
Degree 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 should
When being considered as belonging to the scope of patent protection that determined by the claims submitted to of the present invention.
Claims (10)
1. a kind of Graphene 3D printing material with high impact strength, it is characterised in that in units of weight portion including following
Raw material：Graphene 5.5-7.7 parts, waste plastic 24.6-31 parts, polylactic acid 34.2-40 parts, six PA 800K 11.6-23 parts, ring
Oxypropylene acid esters 18.3-24 parts, specific syntheticses 9.2-18 parts, Starch synthesis agent 5.2-9 parts；
The specific syntheticses are 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 is 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 the isopropylformic acid. of azo two (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 described Graphene 3D printing material with high impact strength, comprises the following steps：
S1：Two-dimensional graphene raw material is purchased on market, 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
It is lower by plastic crushing 2-3h, the plastic grains of 400-600 mesh are obtained after sieving；
S4：Polylactic acid, six polyphosphoric acids are added in primary graphene powder, plastic grains obtained in step S3 obtained in step S1
Potassium, epoxy acrylate, specific syntheticses, are warming up to 194-220 DEG C, and the stirring in the case where rotating speed is 200-400r/min melts 2.2-
3.4h, 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 into 117-128 DEG C, are 100-200r/ in rotating speed
68-82min is reacted under min, material A is obtained；
S42：Add in material A obtained in step S41 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, be in rotating speed
145-232min is reacted under 300-400r/min, material B is obtained；
S43：Add in material B obtained in step S42 and be cooled to 108-125 after plasticizer a, terminator, stabilizer a mixing
DEG C, 62-135min is reacted in the case where rotating speed is 200-300r/min, specific syntheticses are obtained；
S5：The Graphene 3D printing secondary-material being modified 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, Jing extruding strands are obtained the Graphene 3D printing material with high impact strength；
The preparation method of the Starch synthesis agent, comprises the following steps：
S51：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 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 anti-to carry out cross-linked graft under 70-100r/min
2.5-3.5h is answered, slurry b is obtained；
S53：Paste agent is added in slurry b obtained in step S52, 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, are then 55-61 DEG C in temperature, and stirring turns
Speed is obtained slurry c to carry 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, be warming up to 73-77 DEG C, paste
Change 50-55min, gelatinizing is down to 30-33 DEG C after terminating, add defoamer, in the case where rotating speed is 90-130r/min 8-12min stirred,
Prepared Starch synthesis agent.
2. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the tune
Section agent is ACR.
3. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the propellant
For aerogel generating agent.
4. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the coupling agent
A is Silane coupling agent KH550.
5. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the compatilizer
Compatilizer is grafted for maleic anhydride.
6. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the plasticizer
A is dicyclohexyl phthalate.
7. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the antioxidation
Agent is Ronotec17.
8. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the flocculation agent
For aluminium polychlorid.
9. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that the terminator
For wood tar.
10. there is according to claim 1 the Graphene 3D printing material of high impact strength, it is characterised in that described stable
Agent a is rare-earth stabilizer.
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