CN107365508A - A kind of preparation method of environment-friendly materials - Google Patents

Abstract

The invention discloses a kind of preparation method of environment-friendly materials, the environment-friendly materials, including following raw material：Banana stalks, waste plastic, PLA, PTPP, graphene, triethanolamine soap, complexing agent A, complexing agent B, the environment-friendly materials are by preparing banana stalks powder, plastic grains, activated graphene energy powder, 3D printing primary material, mixing, be squeezed into made of the steps such as bar.The present invention can fully recycle banana stalks and waste plastic, expand the application of banana stalks and waste plastic, improve the added value of banana stalks and waste plastic.

Description

A kind of preparation method of environment-friendly materials

【Technical field】

The invention belongs to 3D printing technical field of material, and in particular to a kind of preparation method of environment-friendly materials.

【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 is in the late two decades because coal, electricity, natural gas are popularized, respectively Kind industrial product is enriched, and rural area is reduced to the demand of banana stalks, and banana stalks are processed into for a serious social concern, Many local peasants are still directly burnt banana stalks in the ground, trigger air pollution, fire, aircraft can not be after Normal Take-Off And Landing etc. Fruit.Not only production cost is low for banana stalks 3D printing material, also reduces the discharge capacity of carbon dioxide.Banana stalks are reclaimed, solve agriculture The waste of crop resource, 3D printing material is translated into, expands the application of banana stalks, improve the added value of banana stalks, Have great importance.

Plastics are that a kind of crystallinity is high, nonpolar thermoplastic resin.It has good heat resistance and cold resistance, chemistry Stability is good, also has higher a rigidity and toughness, and mechanical strength is good.The production technology of plastic products has hollow blow molding, injection With extrusion etc., its product form includes various containers, net, strap, cable coating, tubing, profile shapes, sheet material etc..

Using waste plastic as the raw material for preparing 3D printing material, this can not only substantially reduce production cost, while can To reduce environmental pollution, economize on resources, promote resource circulation utilization.

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 preparation method of environment-friendly materials, to solve existing banana stalks resource and waste plastic waste etc. Problem.The present invention can fully recycle banana stalks and waste plastic, expand the application of banana stalks and waste plastic, carry The high added value of banana stalks and waste plastic.

To solve above technical problem, the present invention uses following technical scheme：

A kind of preparation method of environment-friendly materials, 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：Preliminary crushing is carried out to waste plastic using duroplasts disintegrating machine, followed by batch type plastic cleaning Machine is thoroughly cleaned the waste plastic of broken mistake, removes the dirt on surface, and after natural air drying is selected, selected plastics are made；

S3：Selected plastics made from 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 200-300 mesh are obtained after sieving；

S4：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；

S5：Triethanolamine soap is added into energy graphene made from step S4 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；

S6：Plastic grains made from step S3 are added into banana stalks powder made from step S1, are lived made from step S5 Graphite alkene energy powder, PLA, PTPP, complexing agent A, are warming up to 225 DEG C, are stirred in the case where rotating speed is 300r/min 2.8h, room temperature is subsequently cooled to, 3D printing primary material is made；

The preparation method of the complexing agent A, comprises the following steps：

S61：By aerogel generating agent, coupling agent kh-550, fatty glyceride, modified polyacrylate, antioxidant 1010 mixing are warming up to 130 DEG C, react 65min in the case where rotating speed is 200r/min, material A is made；

S62：160 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S41 DEG C, 142min is reacted in the case where rotating speed is 400r/min, material B is made；

S63：122 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S42 DEG C, 60min is reacted in the case where rotating speed is 300r/min, complexing agent A is made；

S7：Crushed at being -115 DEG C in temperature by banana stalks 3D printing primary material made from step S6, add complexing agent B It is well mixed, well mixed mixture is put into screw extruding forming machine, is 205 DEG C in temperature, rotating speed is under 115r/min, Through extruding strand, environment-friendly materials are made；

The preparation method of the complexing agent B, comprises the following steps：

S71：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；

S73：Potassium hydroxide is added into slurry b made from step S72, 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；

S74：Stearic acid file will be added in slurry c made from step S73, 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 B.

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.

Plastics are that a kind of crystallinity is high, nonpolar thermoplastic resin.It has good heat resistance and cold resistance, chemistry Stability is good, also has higher a rigidity and toughness, and mechanical strength is good.The production technology of plastic products has hollow blow molding, injection With extrusion etc., its product form includes various containers, net, strap, cable coating, tubing, profile shapes, sheet material etc..Useless Plastics are abandoned as the raw material for preparing 3D printing material, this can not only substantially reduce production cost, while can reduce environment dirt Dye, economizes on resources, and promotes resource circulation utilization.

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 ".

Triethanolamine soap is a kind of surfactant of function admirable, active matter content >=50%.

Complexing agent A can improve mutability, elasticity and toughness of 3d printed materials etc..

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.

Fatty glyceride can be used for powdery paints, be also used for thermohardening lacquer, adhesive, rubber and modifier, The adhesive of 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.

Complexing agent B can improve the crash resistance of 3d printed materials, reduce fragility.

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 environment-friendly materials produced by the present invention and elongation at break are more excellent, have respectively reached 62.73- 68.43MPa, 50.16%-52.50%；

(2) existed from embodiment 3 and comparative example 1-4 data, graphene, triethanolamine soap, complexing agent A, complexing agent B The tensile strength and elongation at break for improving environment-friendly materials serve synergy；This is probably that graphene is with very high strength Material, graphene is modified by triethanolamine soap surfactant, is merged beneficial to other components, and complexing agent A, compound Agent B addition can improve the mutability of 3D printing material, elasticity, toughness, crash resistance etc..Therefore, by adding graphene, three second Hydramine soap, complexing agent A, complexing agent B, which can act synergistically, improves the tensile strength and elongation at break of 3D printing material；

(3) from embodiment 3 and comparative example 5-7 data, step S2 and step S3 graphene, which fill, can handle and live Change processing and serve synergy in the tensile strength and elongation at break for improving environment-friendly materials；This is probably graphene by three Ethanolamine soap is surfactant-modified, is merged beneficial to other components, in addition graphene fills can handle after can improve graphene Energy, the performance of material is improved, therefore, step S2 and step S3 graphene, which fill, to be handled and activation process synergy improves The tensile strength and elongation at break of 3D printing material；

(4) lack complexing agent A and complexing agent B simultaneously in raw material, then can not make 3d printed materials, and only lack in raw material multiple Mixture A or complexing agent B, do not influence that 3d printed materials are made；

(5) present invention can fully recycle banana stalks and waste plastic, expand the application of banana stalks and waste plastic Scope, improve the added value of banana stalks and waste plastic.

【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.

Embodiment 1

A kind of environment-friendly materials, in units of parts by weight, including following raw material：112 parts of banana stalks, 32 parts of waste plastic, gather 60 parts of lactic acid, 35 parts of PTPP, 1 part of graphene, 0.4 part of triethanolamine soap, 4.3 parts of complexing agent A, complexing agent B 3.5 Part；

The complexing agent A is in units of parts by weight, including following raw material：6 parts of ACR foaming control agents, aerogel generating agent 4 Part, 3 parts of coupling agent kh-550,2 parts of fatty glyceride, 4.2 parts of modified polyacrylate, (the 2- ethyls of phthalic acid two Oneself) 2 parts of ester, 3 parts of antioxidant 1010,4 parts of aluminium polychloride；

The complexing agent B 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 described environment-friendly materials, 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：Preliminary crushing is carried out to waste plastic using duroplasts disintegrating machine, followed by batch type plastic cleaning Machine is thoroughly cleaned the waste plastic of broken mistake, removes the dirt on surface, and after natural air drying is selected, selected plastics are made；

S3：Selected plastics made from 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 300 mesh are obtained after sieving；

S4：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；

S5：Triethanolamine soap is added into energy graphene made from step S4 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；

S6：Plastic grains made from step S3 are added into banana stalks powder made from step S1, are lived made from step S5 Graphite alkene energy powder, PLA, PTPP, complexing agent A, are warming up to 180 DEG C, are stirred in the case where rotating speed is 200r/min 3.3h, room temperature is subsequently cooled to, 3D printing primary material is made；

The preparation method of the complexing agent A, comprises the following steps：

S61：By aerogel generating agent, coupling agent kh-550, fatty glyceride, modified polyacrylate, antioxidant 1010 mixing are warming up to 115 DEG C, react 84min in the case where rotating speed is 100r/min, material A is made；

S62：140 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S61 DEG C, 235min is reacted in the case where rotating speed is 300r/min, material B is made；

S63：105 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S62 DEG C, 136min is reacted in the case where rotating speed is 200r/min, complexing agent A is made；

S7：Crushed at being -92 DEG C in temperature by banana stalks 3D printing primary material made from step S7, add complexing agent B It is well mixed, 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, environment-friendly materials are made；

The preparation method of the complexing agent B, comprises the following steps：

S71：Compound concentration is 22Be ', and pH value is 3.2 para arrowroot slurry a；

S72：The dimethylphosphite, N- ethyl -5- first that concentration is 5.5% 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 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；

S73：Potassium hydroxide is added into slurry b made from step S72, 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；

S74：Stearic acid file will be added in slurry c made from step S73, 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 B.

Embodiment 2

A kind of environment-friendly materials, in units of parts by weight, including following raw material：175 parts of banana stalks, 40 parts of waste plastic, gather 74 parts of lactic acid, 52 parts of PTPP, 2 parts of graphene, 0.6 part of triethanolamine soap, 8.4 parts of complexing agent A, complexing agent B 5.6 Part；

The complexing agent A is in units of parts by weight, including following raw material：9 parts of ACR foaming control agents, aerogel generating agent 5 Part, 4 parts of coupling agent kh-550,3 parts of fatty glyceride, 5.2 parts of modified polyacrylate, (the 2- ethyls of phthalic acid two Oneself) 3 parts of ester, 4 parts of antioxidant 1010,5 parts of aluminium polychloride；

The complexing agent B 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 described environment-friendly materials, 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：Preliminary crushing is carried out to waste plastic using duroplasts disintegrating machine, followed by batch type plastic cleaning Machine is thoroughly cleaned the waste plastic of broken mistake, removes the dirt on surface, and after natural air drying is selected, selected plastics are made；

S3：Selected plastics made from 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 200 mesh are obtained after sieving；

S4：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；

S5：Triethanolamine soap is added into energy graphene made from step S4 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；

S6：Plastic grains made from step S3 are added into banana stalks powder made from step S1, are lived made from step S5 Graphite alkene energy powder, PLA, PTPP, complexing agent A, 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 A, comprises the following steps：

S61：By aerogel generating agent, coupling agent kh-550, fatty glyceride, modified polyacrylate, antioxidant 1010 mixing are warming up to 122 DEG C, react 65min in the case where rotating speed is 200r/min, material A is made；

S62：150 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S61 DEG C, 180min is reacted in the case where rotating speed is 400r/min, material B is made；

S63：112 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S62 DEG C, 100min is reacted in the case where rotating speed is 300r/min, complexing agent A is made；

S7：Crushed at being -100 DEG C in temperature by banana stalks 3D printing primary material made from step S6, add complexing agent B It is 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 strand, environment-friendly materials are made；

The preparation method of the complexing agent B, comprises the following steps：

S71：Compound concentration is 25Be ', and pH value is 3.5 para arrowroot slurry a；

S72：The dimethylphosphite, N- ethyl -5- first that concentration is 6.5% 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 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；

S73：Potassium hydroxide is added into slurry b made from step S72, 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；

S74：Stearic acid file will be added in slurry c made from step S33, 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 B.

Embodiment 3

A kind of environment-friendly materials, in units of parts by weight, including following raw material：176 parts of banana stalks, 40 parts of waste plastic, gather 75 parts of lactic acid, 52 parts of PTPP, 2 parts of graphene, 0.6 part of triethanolamine soap, 8.5 parts of complexing agent A, complexing agent B 5.6 Part；

The complexing agent A is in units of parts by weight, including following raw material：10 parts of ACR foaming control agents, aerogel generating agent 6 parts, 5 parts of coupling agent kh-550,4 parts of fatty glyceride, 6 parts of modified polyacrylate, phthalic acid two (2- ethyl hexyls) 4 parts of ester, 5 parts of antioxidant 1010,6 parts of aluminium polychloride；

The complexing agent B 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 described environment-friendly materials, 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：Preliminary crushing is carried out to waste plastic using duroplasts disintegrating machine, followed by batch type plastic cleaning Machine is thoroughly cleaned the waste plastic of broken mistake, removes the dirt on surface, and after natural air drying is selected, selected plastics are made；

S3：Selected plastics made from 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 200-300 mesh are obtained after sieving；

S4：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；

S5：Triethanolamine soap is added into energy graphene made from step S4 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；

S6：Plastic grains made from step S3 are added into banana stalks powder made from step S1, are lived made from step S5 Graphite alkene energy powder, PLA, PTPP, complexing agent A, are warming up to 225 DEG C, are stirred in the case where rotating speed is 300r/min 2.8h, room temperature is subsequently cooled to, 3D printing primary material is made；

The preparation method of the complexing agent A, comprises the following steps：

S61：By aerogel generating agent, coupling agent kh-550, fatty glyceride, modified polyacrylate, antioxidant 1010 mixing are warming up to 130 DEG C, react 65min in the case where rotating speed is 200r/min, material A is made；

S62：160 are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S41 DEG C, 142min is reacted in the case where rotating speed is 400r/min, material B is made；

S63：122 are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S42 DEG C, 60min is reacted in the case where rotating speed is 300r/min, complexing agent A is made；

S7：Crushed at being -115 DEG C in temperature by banana stalks 3D printing primary material made from step S6, add complexing agent B It is well mixed, well mixed mixture is put into screw extruding forming machine, is 205 DEG C in temperature, rotating speed is under 115r/min, Through extruding strand, environment-friendly materials are made；

The preparation method of the complexing agent B, comprises the following steps：

S71：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；

S73：Potassium hydroxide is added into slurry b made from step S72, 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；

S74：Stearic acid file will be added in slurry c made from step S73, 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 B.

Comparative example 1

Preparation technology and implement 3 essentially identical, it is not both that preparing raw material lacks graphene, triethanolamine soap, compound to have only Agent A, complexing agent B.

Comparative example 2

Preparation technology is essentially identical with implementing 3, and it is not both that preparing raw material lacks graphene and triethanolamine soap to have only.

Comparative example 3

Preparation technology is essentially identical with implementing 3, and it is not both that preparing raw material lacks complexing agent A to have only.

Comparative example 4

Preparation technology is essentially identical with implementing 3, and it is not both that preparing raw material lacks complexing agent B to have only.

Comparative example 5

Preparation technology is essentially identical with implementing 3, and it is not both that preparing raw material lacks complexing agent A, complexing agent B to have only.

Comparative example 6

Preparation technology is essentially identical with implementing 3, 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 7

Preparation technology is essentially identical with implementing 3, and it is not both to fill to handle without step S2 graphene to have only.

Comparative example 8

Preparation technology and implement 3 essentially identical, it is not both graphene activation process without step S3 to have only.

Environment-friendly materials performance in embodiment 1-3 is detected, 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 environment-friendly materials produced by the present invention and elongation at break are more excellent, have respectively reached 62.73- 68.43MPa, 50.16%-52.50%；

(2) existed from embodiment 3 and comparative example 1-4 data, graphene, triethanolamine soap, complexing agent A, complexing agent B The tensile strength and elongation at break for improving environment-friendly materials serve synergy；This is probably that graphene is with very high strength Material, graphene is modified by triethanolamine soap surfactant, is merged beneficial to other components, and complexing agent A, compound Agent B addition can improve the mutability of 3D printing material, elasticity, toughness, crash resistance etc..Therefore, by adding graphene, three second Hydramine soap, complexing agent A, complexing agent B, which can act synergistically, improves the tensile strength and elongation at break of 3D printing material；

(3) from embodiment 3 and comparative example 5-7 data, step S2 and step S3 graphene, which fill, can handle and live Change processing and serve synergy in the tensile strength and elongation at break for improving environment-friendly materials；This is probably graphene by three Ethanolamine soap is surfactant-modified, is merged beneficial to other components, in addition graphene fills can handle after can improve graphene Energy, the performance of material is improved, therefore, step S2 and step S3 graphene, which fill, to be handled and activation process synergy improves The tensile strength and elongation at break of 3D printing material；

(4) lack complexing agent A and complexing agent B simultaneously in raw material, then can not make 3d printed materials, and only lack in raw material multiple Mixture A or complexing agent B, do not influence that 3d printed materials are made.

Claims (1)

1. a kind of preparation method of environment-friendly materials, it is characterised in that comprise the following steps：

S1：The banana stalks of selection are crushed, cross 300 mesh sieve, powder is made, the powder dries 2.2h, control at 105 DEG C Banana stalks powder is made 0.7% in moisture；

S2：Preliminary crushing is carried out to waste plastic using duroplasts disintegrating machine, will followed by batch type plastic cleaning machine The waste plastic crushed is thoroughly cleaned, and removes the dirt on surface, and after natural air drying is selected, selected plastics are made；

S3：Selected plastics made from 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 200-300 mesh are obtained after sieving；

S4：In magnetic field intensity it is 6800GS by graphene, ultrasonic power 600W, temperature is 55 DEG C, rotating speed 300r/min Under, 16min is stirred, energy graphene is made；

S5：Triethanolamine soap is added into energy graphene made from step S4 to be modified, and is 76 DEG C in temperature, rotating speed 150r/ 0.8h is activated under min, activated graphene energy powder is made；

S6：Plastic grains made from step S3, living fossil made from step S5 are added into banana stalks powder made from step S1 Black alkene energy powder, PLA, PTPP, complexing agent A, are warming up to 225 DEG C, are stirred in the case where rotating speed is 300r/min 2.8h, room temperature is subsequently cooled to, 3D printing primary material is made；

The preparation method of the complexing agent A, comprises the following steps：

S61：Aerogel generating agent, coupling agent kh-550, fatty glyceride, modified polyacrylate, antioxidant 1010 are mixed Conjunction is warming up to 130 DEG C, reacts 65min in the case where rotating speed is 200r/min, material A is made；

S62：160 DEG C are warming up to after ACR foaming control agents, aluminium polychloride mixing are added into material A made from step S41, 142min is reacted in the case where rotating speed is 400r/min, material B is made；

S63：122 DEG C are cooled to after the mixing of phthalic acid two (2- ethyl hexyls) ester is added into material B made from step S42, 60min is reacted in the case where rotating speed is 300r/min, complexing agent A is made；

S7：Crushed at being -115 DEG C in temperature by banana stalks 3D printing primary material made from step S6, add complexing agent B mixing 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, environment-friendly materials are made；

The preparation method of the complexing agent B, comprises the following steps：

S71：Compound concentration is 28Be ', and pH value is 3.7 para arrowroot slurry a；

S72：Into starch slurry a made from step S71 add concentration be 7.8% dimethylphosphite, N- ethyl -5- methyl - 2- (1- Methylethyls) hexamethylene formamide, aluminium titanium composite coupler, vanadic anhydride, it is then 59 DEG C in temperature, speed of agitator 3.8h is reacted to carry out cross-linked graft under 80r/min, slurry b is made；

S73：Add potassium hydroxide into slurry b made from step S72, regulation pH value is 9.6, 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 60 DEG C in temperature, speed of agitator is Cross-linking reaction 1.3h is carried out under 120r/min, slurry c is made；

S74：Stearic acid file will be added in slurry c made from step S73, 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 B.