CN107418238A - A kind of printing consumptive material of graphene-containing and preparation method thereof - Google Patents
A kind of printing consumptive material of graphene-containing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses printing consumptive material of a kind of graphene-containing and preparation method thereof, the printing consumptive material is in units of parts by weight, including following raw material：130 parts of banana stalks, 32 parts of kaolin, 70 parts of PLA, 30 parts of PTPP, 1.6 parts of graphene, 8 parts of AESA, 0.7 part of triethanolamine soap, I 6.5 parts of complexing agent, II 5 parts of complexing agent, the printing are by preparing banana stalks powder, modified kaolin, activated graphene energy powder, 3D printing primary material, mixing, be squeezed into made of the steps such as bar with consumptive material.The printing consumptive material of the graphene-containing of the present invention has high tensile and elongation at break, can be applied in 3d printings.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of printing consumptive material of graphene-containing and
Its preparation method.
【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 banana stalks etc. can jointing material, come the technology of constructed object by way of successively printing.3D printing is typically to use number
Word 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
The direct manufacture of some products, there are the parts formed using the printing of this technology, the technology is in jewelry, footwear, industry
Design, building, engineering and construction (AEC), automobile, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System, building
Engineering, gun and other field have all been applied.Although 3D printing technique has above-mentioned technical advantage, from other sides
For face, certain inferior position again be present, in terms of emphasis is embodied in material, it may be said that it is a very big short slab, description of materials
It is poor, it is expensive, directly govern overall development.For technical standpoint, 3D printing is not the difficult technology of a profundity,
Its difference with common print is that printed material.The Object of Israel is the company for grasping most printed materials, and it is
Through can use 14 kinds of stocks and on this basis it is mashed up go out 107 kinds of materials, the mashed up uses of two kinds of materials, colouring are also
Through realizing.But these material categorys also differ greatly compared with routine use material, moreover, the price of these materials
Cheap hundreds of yuan one kilogram, expensive wants 40,000 yuan or so.
China in the late two decades due to coal, electricity, the popularizing of natural gas, various industrial products it is abundant, rural area is to banana stalks
Demand reduce, banana stalks are processed into for a serious social concern, and many local peasants are still directly fired in the ground
Banana stalks are burnt, trigger air pollution, fire, aircraft can not the consequence such as Normal Take-Off And Landing.Banana stalks 3D printing material is not only produced into
This is low, also reduces the discharge capacity of carbon dioxide.Banana stalks are reclaimed, the waste of crop genetic resource is solved, is translated into 3D and beats
Material is printed, expands the application of banana stalks, improves the added value of banana stalks, have great importance.
Clay one of using earliest inorganic material, has the advantages of storage is abundant, cost is cheap as the mankind, so far according to
It is so to apply most inorganic material in people's life, clay cannot be only used for the firing of ceramic material, and house is built, lays road
Road etc., moreover it can be used to industrial, processing, the smelting of metal of filler, waste water in such as high polymer material.With 3D printing technique
Development, various materials are applied to 3D printing, and the application method of traditional material is also changed, and 3D printing technique goes out
Existing, the application method for being similarly clay provides new thinking.When using 3D printing technique forming ceramic products, people
The 3D printing material used is all to fire the ceramic powders formed by clay, is then made pottery by direct or indirect method
Porcelain products, but the preparation method of ceramic powders is complex and high cost high, seriously hinders 3D printing technique in ceramics shaping
Development and application.Clay has excellent viscosity and plasticity in itself, can straight forming ceramic body is made, then sintering obtain
Ceramics, but the defects of due to method, technology, the ceramic idiosome of shaping has the shortcomings of simple in construction, poor dimensional precision, serious limit
The application of clay and its product in life is made, if 3D printing technique is used to clay and then is molded to obtain ceramics, completely
It can improve and solve the defects of above-mentioned, therefore, clay is used for 3D printing and is molded the answering in life to clay and its product
With significant and market value.
It is not suitable for 3D printing shaping without the clay material of modification, the clay mechanical property of high-ductility is poor,
The support and moulding being unfavorable in forming process, and the good clay caking property of mechanical property and plasticity are poor, are unfavorable for being molded
Bonding and extrusion in journey, it is then desired to be modified processing to clay, obtain being suitable for the clay material of 3D printing technique
Material, is the precondition that clay can be used for 3D printing technique.
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, fracture strength are more taller than best steel
200 times.It has good elasticity again simultaneously, and stretch range can reach the 20% of own dimensions.It is that current nature is most thin, strong
Highest material is spent, if making hammock with the graphene of one piece of 1 square metre of area, weight itself can be to hold less than 1 milligram
By one one kilogram of cat.
A kind of novel nano-material most strong as 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 technology new industrial revolution have swept the globe.
【The content of the invention】
The present invention provides a kind of printing consumptive material of graphene-containing and preparation method thereof, to solve existing banana stalks resource wave
The problems such as taking.The present invention can fully recycle banana stalks and kaolin, expand banana stalks and kaolinic application, carry
High banana stalks and kaolinic added value.
To solve above technical problem, the present invention uses following technical scheme：
A kind of printing consumptive material of graphene-containing, in units of parts by weight, including following raw material：130 parts of banana stalks, kaolinite
32 parts of soil, 70 parts of PLA, 30 parts of PTPP, 1.6 parts of graphene, 8 parts of AESA, three ethanol
0.7 part of amine soap, I 6.5 parts of complexing agent, II 5 parts of complexing agent；
The complexing agent I is in units of parts by weight, including following raw material：2.5 parts of GMA, it is modified
5.4 parts of polyacrylate, 3.2 parts of phthalic acid two (2- ethyl hexyls) ester, 3 parts of antioxidant 1076,5.3 parts of aluminium polychloride,
4 parts of ACR foaming control agents, 3 parts of aerogel generating agent, 4.5 parts of coupling agent kh-550；
The complexing agent II is in units of parts by weight, including following raw material：165 parts of tapioca, dimethylphosphite 20
Part, 8 parts of N- ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide, 9 parts of epoxy bromopropane, 2.5 parts of carbonyl diamide, hydrogen-oxygen
Change 2.5 parts of potassium, 0.8 part of aluminium titanium composite coupler, 0.2 part of the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, vanadic anhydride 0.4
Part, 0.5 part of stearic acid file, 0.6 part of dimethyl silicone polymer, 1 part of dibutyl phthalate, methyl methacrylate-fourth two
0.9 part of alkene-styrene copolymer, 0.7 part of modified rosin resin, 0.6 part of boric acid, 0.3 part of ammonium dihydrogen phosphate.
The present invention also provides a kind of preparation method of the printing consumptive material of graphene-containing, comprises the following steps：
S1：The banana stalks of selection are crushed, cross 300 mesh sieve, powder is made, the powder dries 2.8h at 103 DEG C,
Control moisture that banana stalks powder is made 0.9%；
S2：It is 10.8 to take pH, and the kaolin that water content is 2.8% crushed 300 mesh sieve, kaolin powder be made, then
It is modified using AESA, modified kaolin is made；
S3：In magnetic field intensity it is 5800GS by graphene, ultrasonic power 420W, temperature is 48 DEG C, rotating speed 300r/
Under min, stirring 28, energy graphene is made；
S4：Triethanolamine soap is added into energy graphene made from step S3 to be modified, and is 64 DEG C in temperature, rotating speed is
1.2h is activated under 120r/min, activated graphene energy powder is made；
S5：Modified kaolin made from step S2 is added into banana stalks powder made from step S1, made from step S4
Activated graphene energy powder, PLA, PTPP, complexing agent I, are warming up to 200 DEG C, are stirred in the case where rotating speed is 300r/min
4.3h is mixed, is subsequently cooled to room temperature, 3D printing primary material is made；
The preparation method of the complexing agent I, comprises the following steps：
S51：By aerogel generating agent, coupling agent kh-550, GMA, modified polyacrylate,
Antioxidant 1076 mixing is warming up to 1125 DEG C, reacts 75min in the case where rotating speed is 200r/min, material A is made；
S52：150 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S51
DEG C, 195min is reacted in the case where rotating speed is 400r/min, material B is made；
S53：115 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S52
DEG C, 103min is reacted in the case where rotating speed is 300r/min, complexing agent I is made；
S6：Crushed at being -100 DEG C in temperature by 3D printing primary material made from step S5, add complexing agent II and mix
Uniformly, well mixed mixture is put into screw extruding forming machine, is 185 DEG C in temperature, rotating speed is under 108r/min, through squeezing
Silk pressing bar, the printing consumptive material of graphene-containing is made；
The preparation method of the complexing agent II, comprises the following steps：
S61：Compound concentration is 25Be ', and pH value is 3.5 para arrowroot slurry a；
S62：The dimethylphosphite, N- ethyl -5- first that concentration is 6.5% are added into starch slurry a made from step S61
Base -2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 50 DEG C in temperature, stirring turns
Speed is to carry out cross-linked graft under 100r/min to react 3.2h, and slurry b is made；
S63：Potassium hydroxide is added into slurry b made from step S62, regulation pH value is 9.5, is subsequently added into epoxy bromine third
Alkane, carbonyl diamide, the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, dibutyl phthalate, methyl methacrylate-fourth
Diene-styrene copolymer, modified rosin resin, boric acid, ammonium dihydrogen phosphate, it is then 58 DEG C in temperature, speed of agitator
To carry out cross-linking reaction 2.1h under 100r/min, slurry c is made；
S64：Stearic acid file will be added in slurry c made from step S63, regulation pH value is 8.7, is warming up to 75 DEG C, gelatinization
52min, gelatinization are down to 28 DEG C after terminating, add dimethyl silicone polymer, stir 11min in the case where rotating speed is 110r/min, are made
Complexing agent II.
The effect of present component is as follows：
Banana stalks, it is a kind of good fibrous material, develops a kind of degradable 3D that can make full use of discarded banana stalks and beat
Material is printed, can both make full use of the byproduct stalk of crops, and can makes the material after printing will not as degradation material
Because of abandoning white pollution is caused to ecological environment.
Kaolin has excellent viscosity and plasticity in itself, is not suitable for 3D printing without the kaolin of modification
Shaping, the clay mechanical property of high-ductility is poor, the support and moulding being unfavorable in forming process, and the kaolinite that mechanical property is good
Soil knot property and plasticity are poor, the bonding and extrusion being unfavorable in forming process, it is then desired to processing is modified to kaolin,
Obtain being suitable for the kaolin material of 3D printing technique.
PLA is also referred to as polylactide, belongs to polyester family.PLA obtains by main polymerizable raw material of lactic acid
Polymer, raw material sources are abundant and can regenerate.The production process of PLA is pollution-free, and product can be biodegradable,
The circulation in nature is realized, therefore is preferable Green Polymer Material.The heat endurance of PLA is good, processing temperature
170-230 DEG C, the solvent resistance having had, it can be processed with various ways, such as extruding, spinning, biaxial stretch-formed, injection-blow molding.
Made of the PLA product except can it is biodegradable in addition to, biocompatibility, glossiness, the transparency, feel and heat-resist.
PTPP is a kind of mineral surfaces activating agent, has the property of certain organic matter surfactant.
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, fracture strength are more taller than best steel
200 times.It has good elasticity again simultaneously, and stretch range can reach the 20% of own dimensions.It is that current nature is most thin, strong
Highest material is spent, a kind of most strong novel nano-material of electrical and thermal conductivity performance, graphene is referred to as " dark fund ", is " new material
King ".
AESA is a kind of amino acid surfactant of new function admirable, active matter
Content 30%-25%, faint yellow or white paste, when 40%, viscosity improves quickly, forms colloid.
Triethanolamine soap is a kind of surfactant of function admirable, active matter content >=50%.
Complexing agent I can improve mutability, elasticity and toughness of 3d printed materials etc..
GMA is mainly used in powdery paints, is also used for thermohardening lacquer, fibre finish, bonding
Agent, antistatic additive, vinyl chloride stabilizer, the adhesive of rubber and modifier, ion exchange resin and printing-ink.
Modified polyacrylate is adhesive, can be used as pressure-sensitive adhesive and thermal sensitivity adhesive.It is resistance to old due to it
It is good to change performance, bonding pollution is small, easy to use, and the increase of its yield is very fast.
(2- ethyl hexyls) ester of phthalic acid two has good compatibility with most of industrial resins, with acetate fiber
Element, polyvinyl acetate partially compatible, it can be used as plasticizer use.
Antioxidant is a kind of chemical substance, in the presence of it is only a small amount of in polymeric system, so that it may delay or suppresses to gather
The progress of compound oxidizing process, so as to prevent the aging of polymer and extend its service life, it is otherwise known as " age resistor ".
Aluminium polychloride is a kind of New Inorganic High Polymer Coagulant, has stronger bridge formation absorption property and cohesion energy
Power.
ACR foaming control agents, which have, promotes the melting of 3d printed materials, improves surface smoothness, improves the elasticity of melt, enhancing
The elongation of melt and the effect of intensity.
Aerogel generating agent refer to it is a kind of easily by the compound for being thermally decomposed into free radical (i.e. primary group of free radicals), available for drawing
Send out alkenes, the radical polymerization of double vinyl monomers and copolymerization, it can also be used to the crosslinking curing and high score of unsaturated polyester (UP)
Sub- cross-linking reaction etc..
Coupling agent kh-550 improves synthetic resin and printed with a kind of 3d of inorganic filler or the interface performance of reinforcing material
Meterial additive, also known as surface modifier.It can reduce the viscosity of molten synthetic resin in material processing, improve filling
The decentralization of agent makes product obtain good surface quality and machinery, heat and electrical property to improve processing characteristics.
Complexing agent II can improve the crash resistance of 3d printed materials, reduce fragility etc..
Tapioca is the powder that cassava dehydrates after starch isolation.Tapioca has ative starch and various
The major class of converted starch two, is widely used in food industry and non-food industries.
Dimethylphosphite is mainly used in organic synthesis.
N- ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide is amide-type nonionic surfactant, has one
Determine the property of organic matter surfactant, make tapioca surface active, with dimethylphosphite occur graft reaction, then with ring
Oxygen N-Propyl Bromide, carbonyl diamide crosslink reaction.
Epoxy bromopropane is a kind of organic compound, is mainly applicable to epoxy resin processed, and a kind of oxygen carrier
Stabilizer and chemical intermediate, the primary raw material of epoxy radicals and phenoxy resin.
Carbonyl diamide can react with epoxy bromopropane.
Potassium hydroxide has extremely strong alkalescence and corrosivity, and its property is similar to caustic soda
A kind of 3d that aluminium titanium composite coupler improves synthetic resin and inorganic filler or the interface performance of reinforcing material is beaten
Print meterial additive, also known as surface modifier.It can reduce the viscosity of molten synthetic resin in material processing, and improvement is filled out
The decentralization of agent is filled to improve processing characteristics, and then product is obtained good surface quality and machinery, heat and electrical property
The isobutyric acid of azo two (acrylic acid ethylene glycol) ester is made a kind of initiator and used.
Vanadic anhydride uses as catalyst.
Stearic acid rasp has a good mobility, and color and luster retentivity is good during processing, product excellent transparency, particularly its photo-thermal
Stability is reached the international leading level, and can effectively keep the recycled of secondary operation.
Dimethyl silicone polymer is made a kind of defoamer and used.
Dibutyl phthalate has good compatibility with most of industrial resins, can be used as plasticizer use.
Methyl methacrylate-butadiene-styrene copolymer is made a kind of toughener and used.
Modified rosin resin is made a kind of tackifier and used.
Boric acid uses as a kind of water resistant additive
Ammonium dihydrogen phosphate uses as a kind of antibacterial.
The invention has the advantages that：
(1) tensile strength of the printing consumptive material of graphene-containing produced by the present invention and elongation at break are more excellent, reach respectively
56.26-62.67MPa, 46.78%-48.62% are arrived；
(2) from embodiment 2 and comparative example 1-5 data, graphene, AESA, three second
Hydramine soap, complexing agent I, complexing agent II are served in the printing for improving graphene-containing with the tensile strength and elongation at break of consumptive material
Synergy；This is probably that graphene is the material for having very high strength, and kaolin passes through AESA
The modification of surfactant, graphene be modified by triethanolamine soap surfactant, is merged beneficial to other components, and answer
The addition of mixture I, complexing agent II can improve the mutabilities of 3d printed materials, elasticity, toughness, crash resistance etc..Therefore, addition is passed through
Graphene, AESA, triethanolamine soap, complexing agent I, complexing agent II, which can act synergistically, improves 3D printing
The tensile strength and elongation at break of material；
(3) from embodiment 2 and comparative example 7-9 data, step S2 and step S3 graphene, which fill, can handle and live
Change processing and serve synergy with the tensile strength and elongation at break of consumptive material in the printing for improving graphene-containing；This is probably
Graphene is modified by triethanolamine soap surfactant, is merged beneficial to other components, after graphene fills and can handled in addition
Graphene energy can be improved, improves the performance of material, therefore, step S2 and step S3 graphene, which fill, can be handled and activation process
Synergy improves the tensile strength and elongation at break of 3D printing material；
(4) from the data of comparative example Isosorbide-5-Nitrae -6, lack complexing agent I and complexing agent II simultaneously in raw material, then can not make 3d
Printed material, and only lack complexing agent I or complexing agent II in raw material, do not influence that 3d printed materials are made；
(5) present invention can fully recycle banana stalks and kaolin, expand banana stalks and kaolinic application,
Improve banana stalks and kaolinic added value.
【Embodiment】
For ease of more fully understanding the present invention, it is illustrated by following examples.
Embodiment 1
A kind of printing consumptive material of graphene-containing, in units of parts by weight, including following raw material：98 parts of banana stalks, kaolinite
28 parts of soil, 63 parts of PLA, 24 parts of PTPP, 1.2 parts of graphene, 6 parts of AESA, three ethanol
0.5 part of amine soap, I 4.5 parts of complexing agent, II 3.6 parts of complexing agent；
The complexing agent I is in units of parts by weight, including following raw material：1.7 parts of GMA, it is modified
4.6 parts of polyacrylate, 2.2 parts of phthalic acid two (2- ethyl hexyls) ester, 2 parts of antioxidant 1076,4.3 parts of aluminium polychloride,
3 parts of ACR foaming control agents, 2 parts of aerogel generating agent, 3.2 parts of coupling agent kh-550；
The complexing agent II is in units of parts by weight, including following raw material：152 parts of tapioca, dimethylphosphite 18
Part, 6 parts of N- ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide, 7 parts of epoxy bromopropane, 1.8 parts of carbonyl diamide, hydrogen-oxygen
Change 1.6 parts of potassium, 0.7 part of aluminium titanium composite coupler, 0.2 part of the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, vanadic anhydride 0.3
Part, 0.4 part of stearic acid file, 0.4 part of dimethyl silicone polymer, 0.8 part of dibutyl phthalate, methyl methacrylate-fourth
0.8 part of diene-styrene copolymer, 0.6 part of modified rosin resin, 0.5 part of boric acid, 0.2 part of ammonium dihydrogen phosphate；
The preparation method of the printing consumptive material of described graphene-containing, comprises the following steps：
S1：The banana stalks of selection are crushed, cross 200 mesh sieve, powder is made, the powder dries 3.5h at 100 DEG C,
Control moisture that banana stalks powder is made 1%；
S2：It is 8.7 to take pH, and the kaolin that water content is 3% crushed 200 mesh sieve, and kaolin powder is made, then uses
AESA is modified, and modified kaolin is made；
S3：In magnetic field intensity it is 5200GS by graphene, ultrasonic power 240W, temperature is 40 DEG C, rotating speed 200/
Under min, 40min is stirred, energy graphene is made；
S4：Triethanolamine soap is added into energy graphene made from step S3 to be modified, and is 52 DEG C in temperature, rotating speed is
1.7h is activated under 60r/min, activated graphene energy powder is made；
S5：Modified kaolin made from step S2 is added into banana stalks powder made from step S1, made from step S4
Activated graphene energy powder, PLA, PTPP, complexing agent I, are warming up to 180 DEG C, are stirred in the case where rotating speed is 200r/min
3.3h is mixed, is subsequently cooled to room temperature, 3D printing primary material is made；
The preparation method of the complexing agent I, comprises the following steps：
S51：By aerogel generating agent, coupling agent kh-550, GMA, modified polyacrylate,
Antioxidant 1076 mixing is warming up to 116 DEG C, reacts 87min in the case where rotating speed is 100/min, material A is made；
S52：140 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S51
DEG C, 238min is reacted in the case where rotating speed is 300r/min, material B is made；
S53：108 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S52
DEG C, 140min is reacted in the case where rotating speed is 200r/min, complexing agent I is made；
S6：Crushed at being -92 DEG C in temperature by 3D printing primary material made from step S5, add complexing agent II and mix
It is even, well mixed mixture is put into screw extruding forming machine, is 168 DEG C in temperature, rotating speed is under 115r/min, through extruding
Strand, the printing consumptive material of graphene-containing is made；
The preparation method of the complexing agent II, comprises the following steps：
S61：Compound concentration is 22Be ', and pH value is 3.2 para arrowroot slurry a；
S62：The dimethylphosphite, N- ethyl -5- first that concentration is 5.5% are added into starch slurry a made from step S61
Base -2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 42 DEG C in temperature, stirring turns
Speed is to carry out cross-linked graft under 80r/min to react 3.8h, and slurry b is made；
S63：Potassium hydroxide is added into slurry b made from step S62, regulation pH value is 9.2, is subsequently added into epoxy bromine third
Alkane, carbonyl diamide, the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, dibutyl phthalate, methyl methacrylate-fourth
Diene-styrene copolymer, modified rosin resin, boric acid, ammonium dihydrogen phosphate, it is then 56 DEG C in temperature, speed of agitator
To carry out cross-linking reaction 3h under 80r/min, slurry c is made；
S64：Stearic acid file will be added in slurry c made from step S63, regulation pH value is 8.4, is warming up to 73 DEG C, gelatinization
55min, gelatinization are down to 26 DEG C after terminating, add dimethyl silicone polymer, stir 13min in the case where rotating speed is 90r/min, are made multiple
Mixture II.
Embodiment 2
A kind of printing consumptive material of graphene-containing, in units of parts by weight, including following raw material：130 parts of banana stalks, kaolinite
32 parts of soil, 70 parts of PLA, 30 parts of PTPP, 1.6 parts of graphene, 8 parts of AESA, three ethanol
0.7 part of amine soap, I 6.5 parts of complexing agent, II 5 parts of complexing agent；
The complexing agent I is in units of parts by weight, including following raw material：2.5 parts of GMA, it is modified
5.4 parts of polyacrylate, 3.2 parts of phthalic acid two (2- ethyl hexyls) ester, 3 parts of antioxidant 1076,5.3 parts of aluminium polychloride,
4 parts of ACR foaming control agents, 3 parts of aerogel generating agent, 4.5 parts of coupling agent kh-550；
The complexing agent II is in units of parts by weight, including following raw material：165 parts of tapioca, dimethylphosphite 20
Part, 8 parts of N- ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide, 9 parts of epoxy bromopropane, 2.5 parts of carbonyl diamide, hydrogen-oxygen
Change 2.5 parts of potassium, 0.8 part of aluminium titanium composite coupler, 0.2 part of the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, vanadic anhydride 0.4
Part, 0.5 part of stearic acid file, 0.6 part of dimethyl silicone polymer, 1 part of dibutyl phthalate, methyl methacrylate-fourth two
0.9 part of alkene-styrene copolymer, 0.7 part of modified rosin resin, 0.6 part of boric acid, 0.3 part of ammonium dihydrogen phosphate；
The preparation method of the printing consumptive material of described graphene-containing, comprises the following steps：
S1：The banana stalks of selection are crushed, cross 300 mesh sieve, powder is made, the powder dries 2.8h at 103 DEG C,
Control moisture that banana stalks powder is made 0.9%；
S2：It is 10.8 to take pH, and the kaolin that water content is 2.8% crushed 300 mesh sieve, kaolin powder be made, then
It is modified using AESA, modified kaolin is made；
S3：In magnetic field intensity it is 5800GS by graphene, ultrasonic power 420W, temperature is 48 DEG C, rotating speed 300r/
Under min, stirring 28, energy graphene is made；
S4：Triethanolamine soap is added into energy graphene made from step S3 to be modified, and is 64 DEG C in temperature, rotating speed is
1.2h is activated under 120r/min, activated graphene energy powder is made；
S5：Modified kaolin made from step S2 is added into banana stalks powder made from step S1, made from step S4
Activated graphene energy powder, PLA, PTPP, complexing agent I, are warming up to 200 DEG C, are stirred in the case where rotating speed is 300r/min
4.3h is mixed, is subsequently cooled to room temperature, 3D printing primary material is made；
The preparation method of the complexing agent I, comprises the following steps：
S51：By aerogel generating agent, coupling agent kh-550, GMA, modified polyacrylate,
Antioxidant 1076 mixing is warming up to 1125 DEG C, reacts 75min in the case where rotating speed is 200r/min, material A is made；
S52：150 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S51
DEG C, 195min is reacted in the case where rotating speed is 400r/min, material B is made；
S53：115 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S52
DEG C, 103min is reacted in the case where rotating speed is 300r/min, complexing agent I is made；
S6：Crushed at being -100 DEG C in temperature by 3D printing primary material made from step S5, add complexing agent II and mix
Uniformly, well mixed mixture is put into screw extruding forming machine, is 185 DEG C in temperature, rotating speed is under 108r/min, through squeezing
Silk pressing bar, the printing consumptive material of graphene-containing is made；
The preparation method of the complexing agent II, comprises the following steps：
S61：Compound concentration is 25Be ', and pH value is 3.5 para arrowroot slurry a；
S62：The dimethylphosphite, N- ethyl -5- first that concentration is 6.5% are added into starch slurry a made from step S61
Base -2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 50 DEG C in temperature, stirring turns
Speed is to carry out cross-linked graft under 100r/min to react 3.2h, and slurry b is made；
S63：Potassium hydroxide is added into slurry b made from step S62, regulation pH value is 9.5, is subsequently added into epoxy bromine third
Alkane, carbonyl diamide, the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, dibutyl phthalate, methyl methacrylate-fourth
Diene-styrene copolymer, modified rosin resin, boric acid, ammonium dihydrogen phosphate, it is then 58 DEG C in temperature, speed of agitator
To carry out cross-linking reaction 2.1h under 100r/min, slurry c is made；
S64：Stearic acid file will be added in slurry c made from step S63, regulation pH value is 8.7, is warming up to 75 DEG C, gelatinization
52min, gelatinization are down to 28 DEG C after terminating, add dimethyl silicone polymer, stir 11min in the case where rotating speed is 110r/min, are made
Complexing agent II.
Embodiment 3
A kind of printing consumptive material of graphene-containing, in units of parts by weight, including following raw material：156 parts of banana stalks, kaolinite
36 parts of soil, 78 parts of PLA, 35 parts of PTPP, 2 parts of graphene, 10 parts of AESA, three ethanol
0.8 part of amine soap, I 8.7 parts of complexing agent, II 6.2 parts of complexing agent；
The complexing agent I is in units of parts by weight, including following raw material：3.5 parts of GMA, it is modified
6.2 parts of polyacrylate, 4 parts of phthalic acid two (2- ethyl hexyls) ester, 4 parts of antioxidant 1076,6.3 parts of aluminium polychloride,
5 parts of ACR foaming control agents, 4 parts of aerogel generating agent, 5.6 parts of coupling agent kh-550；
The complexing agent II is in units of parts by weight, including following raw material：182 parts of tapioca, dimethylphosphite 22
Part, 10 parts of N- ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide, 10 parts of epoxy bromopropane, 4.2 parts of carbonyl diamide, hydrogen
3 parts of potassium oxide, 0.9 part of aluminium titanium composite coupler, 0.3 part of the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, vanadic anhydride 0.5
Part, 0.6 part of stearic acid file, 0.7 part of dimethyl silicone polymer, 1.2 parts of dibutyl phthalate, methyl methacrylate-fourth
1 part of diene-styrene copolymer, 0.8 part of modified rosin resin, 0.7 part of boric acid, 0.4 part of ammonium dihydrogen phosphate；
The preparation method of the printing consumptive material of described graphene-containing, comprises the following steps：
S1：The banana stalks of selection are crushed, cross 300 mesh sieve, powder is made, the powder dries 2.2h at 105 DEG C,
Control moisture that banana stalks powder is made 0.7%；
S2：It is 9.6 to take pH, and the kaolin that water content is 2.4% crushed 300 mesh sieve, and kaolin powder is made, then adopts
It is modified with AESA, modified kaolin is made；
S3：In magnetic field intensity it is 6800GS by graphene, ultrasonic power 600W, temperature is 55 DEG C, rotating speed 300r/
Under min, 16min is stirred, energy graphene is made；
S4：Triethanolamine soap is added into energy graphene made from step S3 to be modified, and is 76 DEG C in temperature, rotating speed is
0.8h is activated under 150r/min, activated graphene energy powder is made；
S5：Modified kaolin made from step S2 is added into banana stalks powder made from step S1, made from step S4
Activated graphene energy powder, PLA, PTPP, complexing agent I, are warming up to 225 DEG C, are stirred in the case where rotating speed is 300r/min
2.8h is mixed, is subsequently cooled to room temperature, 3D printing primary material is made；
The preparation method of the complexing agent I, comprises the following steps：
S51：By aerogel generating agent, coupling agent kh-550, GMA, modified polyacrylate,
Antioxidant 1076 mixing is warming up to 132 DEG C, reacts 69min in the case where rotating speed is 200r/min, material A is made；
S52：160 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S51
DEG C, 145min is reacted in the case where rotating speed is 400r/min, material B is made；
S53：125 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S52
DEG C, 65min is reacted in the case where rotating speed is 300r/min, complexing agent I is made；
S6：Crushed at being -115 DEG C in temperature by 3D printing primary material made from step S5, add complexing agent II and mix
Uniformly, well mixed mixture is put into screw extruding forming machine, is 205 DEG C in temperature, rotating speed is under 115r/min, through squeezing
Silk pressing bar, the printing consumptive material of graphene-containing is made；
The preparation method of the complexing agent II, comprises the following steps：
S61：Compound concentration is 28Be ', and pH value is 3.7 para arrowroot slurry a；
S72：The dimethylphosphite, N- ethyl -5- first that concentration is 7.8% are added into starch slurry a made from step S71
Base -2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 59 DEG C in temperature, stirring turns
Speed is to carry out cross-linked graft under 80r/min to react 3.8h, and slurry b is made；
S63：Potassium hydroxide is added into slurry b made from step S62, regulation pH value is 9.6, is subsequently added into epoxy bromine third
Alkane, carbonyl diamide, the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, dibutyl phthalate, methyl methacrylate-fourth
Diene-styrene copolymer, modified rosin resin, boric acid, ammonium dihydrogen phosphate, it is then 60 DEG C in temperature, speed of agitator
To carry out cross-linking reaction 1.3h under 120r/min, slurry c is made；
S64：Stearic acid file will be added in slurry c made from step S63, regulation pH value is 8.8, is warming up to 77 DEG C, gelatinization
50min, gelatinization are down to 30 DEG C after terminating, add dimethyl silicone polymer, stir 9min in the case where rotating speed is 130r/min, are made multiple
Mixture II.
Comparative example 1
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks graphene, AEO to have only
Ammonium sulfate, triethanolamine soap, complexing agent I, complexing agent II.
Comparative example 2
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks graphene and triethanolamine soap to have only.
Comparative example 3
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks AESA to have only.
Comparative example 4
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks complexing agent I to have only.
Comparative example 5
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks complexing agent II to have only.
Comparative example 6
Preparation method is essentially identical with implementing 2, and it is not both that preparing raw material lacks complexing agent I, complexing agent II to have only.
Comparative example 7
Preparation method is essentially identical with implementing 2, and it is not both to fill to locate without step S2 and step S3 graphene to have only
Reason and activation process.
Comparative example 8
Preparation method is essentially identical with implementing 2, and it is not both to fill to handle without step S2 graphene to have only.
Comparative example 9
Preparation method and implement 2 essentially identical, it is not both graphene activation process without step S3 to have only.
Printing in embodiment 1-3 is detected with consumptive material performance, it is as a result as shown in the table.
By upper table it is recognised that can obtain to draw a conclusion：
(1) tensile strength of 3D printing environment-friendly materials produced by the present invention and elongation at break are more excellent, respectively reach
56.26-62.67MPa, 46.78%-48.62%；
(2) from embodiment 2 and comparative example 1-5 data, graphene, AESA, three second
Hydramine soap, complexing agent I, complexing agent II are served in the printing for improving graphene-containing with the tensile strength and elongation at break of consumptive material
Synergy；This is probably that graphene is the material for having very high strength, and kaolin passes through AESA
The modification of surfactant, graphene be modified by triethanolamine soap surfactant, is merged beneficial to other components, and answer
The addition of mixture I, complexing agent II can improve the mutabilities of 3d printed materials, elasticity, toughness, crash resistance etc..Therefore, addition is passed through
Graphene, AESA, triethanolamine soap, complexing agent I, complexing agent II, which can act synergistically, improves 3D printing
The tensile strength and elongation at break of material；
(3) from embodiment 2 and comparative example 7-9 data, step S2 and step S3 graphene, which fill, can handle and live
Change processing and serve synergy with the tensile strength and elongation at break of consumptive material in the printing for improving graphene-containing；This is probably
Graphene is modified by triethanolamine soap surfactant, is merged beneficial to other components, after graphene fills and can handled in addition
Graphene energy can be improved, improves the performance of material, therefore, step S2 and step S3 graphene, which fill, can be handled and activation process
Synergy improves the tensile strength and elongation at break of 3D printing material；
(4) from the data of comparative example Isosorbide-5-Nitrae -6, lack complexing agent I and complexing agent II simultaneously in raw material, then can not make 3d
Printed material, and only lack complexing agent I or complexing agent II in raw material, do not influence that 3d printed materials are made.
Claims (2)
- A kind of 1. printing consumptive material of graphene-containing, it is characterised in that in units of parts by weight, including following raw material：Banana stalks 130 parts, 32 parts of kaolin, 70 parts of PLA, 30 parts of PTPP, 1.6 parts of graphene, AESA 8 parts, 0.7 part of triethanolamine soap, I 6.5 parts of complexing agent, II 5 parts of complexing agent；The complexing agent I is in units of parts by weight, including following raw material：2.5 parts of GMA, modified poly- third 5.4 parts of olefin(e) acid ester, 3.2 parts of phthalic acid two (2- ethyl hexyls) ester, 3 parts of antioxidant 1076,5.3 parts of aluminium polychloride, ACR 4 parts of foaming control agent, 3 parts of aerogel generating agent, coupling agent kh-5504.5 parts；The complexing agent II is in units of parts by weight, including following raw material：165 parts of tapioca, 20 parts of dimethylphosphite, N- 8 parts of ethyl -5- methyl -2- (1- Methylethyls) hexamethylene formamide, 9 parts of epoxy bromopropane, 2.5 parts of carbonyl diamide, potassium hydroxide 2.5 parts, 0.8 part of aluminium titanium composite coupler, 0.2 part of the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, 0.4 part of vanadic anhydride, 0.5 part of stearic acid file, 0.6 part of dimethyl silicone polymer, 1 part of dibutyl phthalate, methyl methacrylate-fourth two 0.9 part of alkene-styrene copolymer, 0.7 part of modified rosin resin, 0.6 part of boric acid, 0.3 part of ammonium dihydrogen phosphate.
- A kind of 2. preparation method of the printing consumptive material of graphene-containing according to claim 1, it is characterised in that including with Lower step：S1：The banana stalks of selection are crushed, cross 300 mesh sieve, powder is made, the powder dries 2.8h, control at 103 DEG C Banana stalks powder is made 0.9% in moisture；S2：It is 10.8 to take pH, and the kaolin that water content is 2.8% crushed 300 mesh sieve, and kaolin powder is made, then uses AESA is modified, and modified kaolin is made；S3：In magnetic field intensity it is 5800GS by graphene, ultrasonic power 420W, temperature is 48 DEG C, rotating speed 300r/min Under, stirring 28, energy graphene is made；S4：Triethanolamine soap is added into energy graphene made from step S3 to be modified, and is 64 DEG C in temperature, rotating speed 120r/ 1.2h is activated under min, activated graphene energy powder is made；S5：Modified kaolin made from step S2, activation made from step S4 are added into banana stalks powder made from step S1 Graphene energy powder, PLA, PTPP, complexing agent I, are warming up to 200 DEG C, are stirred in the case where rotating speed is 300r/min 4.3h, room temperature is subsequently cooled to, 3D printing primary material is made；The preparation method of the complexing agent I, comprises the following steps：S51：By aerogel generating agent, coupling agent kh-550, GMA, modified polyacrylate, antioxygen The mixing of agent 1076 is warming up to 1125 DEG C, reacts 75min in the case where rotating speed is 200r/min, material A is made；S52：150 DEG C are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S51, 195min is reacted in the case where rotating speed is 400r/min, material B is made；S53：115 DEG C are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S52, 103min is reacted in the case where rotating speed is 300r/min, complexing agent I is made；S6：Crushed at being -100 DEG C in temperature by 3D printing primary material made from step S5, add complexing agent II and be well mixed, Well mixed mixture is put into screw extruding forming machine, is 185 DEG C in temperature, rotating speed is under 108r/min, through extruding silk Bar, the printing consumptive material of graphene-containing is made；The preparation method of the complexing agent II, comprises the following steps：S61：Compound concentration is 25Be ', and pH value is 3.5 para arrowroot slurry a；S62：Into starch slurry a made from step S61 add concentration be 6.5% dimethylphosphite, N- ethyl -5- methyl - 2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 50 DEG C in temperature, speed of agitator 3.2h is reacted to carry out cross-linked graft under 100r/min, slurry b is made；S63：Add potassium hydroxide into slurry b made from step S62, regulation pH value is 9.5, be subsequently added into epoxy bromopropane, Carbonyl diamide, the isobutyric acid of azo two (acrylic acid ethylene glycol) ester, dibutyl phthalate, methyl methacrylate-fourth two Alkene-styrene copolymer, modified rosin resin, boric acid, ammonium dihydrogen phosphate, it is then 58 DEG C in temperature, speed of agitator is Cross-linking reaction 2.1h is carried out under 100r/min, slurry c is made；S64：Stearic acid file will be added in slurry c made from step S63, regulation pH value is 8.7, is warming up to 75 DEG C, gelatinization 52min, gelatinization are down to 28 DEG C after terminating, add dimethyl silicone polymer, stir 11min in the case where rotating speed is 110r/min, are made Complexing agent II.
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| CN113786031A (en) * | 2021-08-26 | 2021-12-14 | 北京工业大学 | 3D printing-based graphene-polydimethylsiloxane piezoelectric energy storage insole design method |
| CN114525039A (en) * | 2022-03-15 | 2022-05-24 | 金美菊 | Graphene modified resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113786031A (en) * | 2021-08-26 | 2021-12-14 | 北京工业大学 | 3D printing-based graphene-polydimethylsiloxane piezoelectric energy storage insole design method |
| CN114525039A (en) * | 2022-03-15 | 2022-05-24 | 金美菊 | Graphene modified resin and preparation method thereof |
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