CN107118501A - A kind of medical corrosion-resistant high tenacity 3D printing material - Google Patents
A kind of medical corrosion-resistant high tenacity 3D printing material Download PDFInfo
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- CN107118501A CN107118501A CN201710463088.4A CN201710463088A CN107118501A CN 107118501 A CN107118501 A CN 107118501A CN 201710463088 A CN201710463088 A CN 201710463088A CN 107118501 A CN107118501 A CN 107118501A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses the medical corrosion-resistant high tenacity 3D printing material of one kind, its raw material includes ABS resin, SAN resins, butadiene rubber, neoprene, epoxy acrylic resin, polymethyl methacrylate, makrolon, polyolefin elastomer, sulphur, sulfur dichloride, chlorinated paraffin, dimethicone, Firebrake ZB, isocyanates, nano-graphite, carbon black, blanc fixe, nano-aluminum hydroxide, polyphosphoric acids aluminium, nano silicon, mica powder, talcum powder, silane coupler KH 560, kodalk, pentaerythrite, PLA, pla-pcl, odium stearate, neopelex, antioxidant, degasser, dimethicone, anti-corrosive aids, modified filler and plasticized modifier.The 3D printing material of the present invention has excellent corrosion-resistant and toughness.
Description
Technical field
The present invention relates to the technical field of 3D printing material, more particularly to a kind of medical corrosion-resistant high tenacity 3D printing material
Material.
Background technology
ABS resin production in the country's is appointed so based on general material with consumption at present, and PP Pipe Compound is mainly by import.With market
Develop rapidly, the general material markets of ABS will further be segmented, gradually form using high rigidity, versatility, impact series of products as
The consumptio of representative.The characteristics of impact ABS resin has high impact strength, is widely used in auto parts, family expenses
In terms of electrical equipment, sporting goods and medical apparatus, market potential is huge.But ABS is as one kind of 3D printing material,
It increases in the consumption of 3D printing technique also with the maturation of 3D printing technique, but is applied to 3D printing skill in the prior art
The toughness and antiseptic property of the ABS material of art can not meet demand during actual use, so needing a kind of medical corrosion resistant of design badly
High tenacity 3D printing material is lost to solve the problems of the prior art.
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of medical corrosion-resistant high tenacity 3D printing
Material, with excellent toughness and antiseptic property.
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
It is 85-125 parts of fat, 20-40 parts of SAN resins, 5-15 parts of butadiene rubber, 3-6 parts of neoprene, 4-8 parts of epoxy acrylic resin, poly-
2-6 parts of methyl methacrylate, 1-4 parts of makrolon, 3-6 parts of polyolefin elastomer, 2-5 parts of sulphur, 1-6 parts of sulfur dichloride,
1-4 parts of chlorinated paraffin, 2-4 parts of dimethicone, 1-5 parts of Firebrake ZB, 3-8 parts of isocyanates, 2-6 parts of nano-graphite, carbon black 3-6
Part, 4-8 parts of blanc fixe, 4-8 parts of nano-aluminum hydroxide, 1-5 parts of polyphosphoric acids aluminium, 2-5 parts of nano silicon, mica powder 3-
5 parts, 3-9 parts of talcum powder, 2-6 parts of silane coupler KH-560,2-8 parts of kodalk, 1-4 parts of pentaerythrite, PLA 2-4
Part, 1-6 parts of pla-pcl, 2-6 parts of odium stearate, 1-4 parts of neopelex, 3-6 parts of antioxidant, 2-5 parts of degasser,
4-6 parts of dimethicone, 3-9 parts of anti-corrosive aids, 2-8 parts of modified filler, 4-9 parts of plasticized modifier.
Preferably, the raw material of anti-corrosive aids includes by weight：3-6 parts of butyl acrylate, nano tin oxide powder 4-8
Part, 3-9 parts of Silane coupling reagent KH-570,2-5 parts of the concentrated sulfuric acid, 5-15 parts of distilled water, 3-6 parts of montmorillonite, 2-8 parts of hydrochloric acid solution,
3-5 parts of calcium sulfate, 1-4 parts of silicon nitride, 2-5 parts of montmorillonite powder, 3-6 parts of barium sulfate, 1-5 parts of antimony trioxide, 3-6 parts of weathered coal,
4-8 parts of seawood meal, 2-8 parts of trbasic zinc phosphate, 3-6 parts of bentonite, 1-4 parts of zeolite powder, 2-8 parts of zirconium oxide.
Preferably, anti-corrosive aids are prepared by following technique：Butyl acrylate and nano tin oxide powder are mixed
Uniformly, Silane coupling reagent KH-570 is then added, 20-28h is stirred in 38-46 DEG C, is cooled to room temperature, is subsequently placed in ice-water bath
Broken, ultrasonically treated 10-14min obtains material a；The concentrated sulfuric acid is scattered in distilled water, stir to obtain acid compound intercalation
The aqueous solution；Montmorillonite is put into calcining furnace and calcines 1-5h at 750-850 DEG C, is cooled down, is put into hydrochloric acid solution and soaks 2-4h,
Filtering is taken out, and with the clean drying of clear water, is ground into 150-350 mesh powder and is then added to acid compound aqueous intercalation solution mixing
It is even, 85-95 DEG C is then heated to, 1-3h is incubated, is subsequently added into material a, calcium sulfate, silicon nitride, montmorillonite powder, barium sulfate, three
Antimony oxide, weathered coal, seawood meal, trbasic zinc phosphate, bentonite, zeolite powder and zirconium oxide are well mixed, surpass in 45-55 DEG C of water-bath
Sound-mechanical agitation disperses 2-4h, and stratification removes supernatant liquor, and lower reaction product layer is carried out into suction filtration, washing, 750-850
DEG C constant weight is dried under vacuum to, ground, crossed 150-250 mesh sieves, that is, obtain anti-corrosive aids.
Preferably, the raw material of modified filler includes by weight：3-6 parts of wood fiber powder, 2-5 parts of bamboo fibre, tapioca starch
4-8 parts, 3-6 parts of maleic anhydride, 2-5 parts of ammonium persulfate, 1-4 parts of styrene, 3-6 parts of potassium acetate, cetyl trimethyl bromination
4-8 parts of ammonium, 2-6 parts of titanate coupling agent.
Preferably, modified filler is prepared by following technique：Under nitrogen protection, by wood fiber powder, bamboo fibre, wood
Potato powder, distilled water and maleic anhydride are well mixed, then heat to 80-90 DEG C, are incubated 10-30min, then add ammonium persulfate
It is well mixed, add styrene after stirring 5-15min and be well mixed, then stir 50-70min in 850-1250r/min rotating speeds,
85-95 DEG C is then heated to, 40-50h is extracted, then in vacuum drying oven, 65-75 DEG C dries to constant weight, and is cooled to room temperature, then
Add potassium acetate to be well mixed, vibrate 3-5min, grind 10-30min, 20-26h is stood, then in 60-80 DEG C of freeze-day with constant temperature
20-28h, grinds, and washes, drying, is subsequently added into cetyl trimethylammonium bromide, titanate coupling agent and water and is well mixed,
80-90 DEG C is heated to, 20-40min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Preferably, modified toughened dose of raw material includes by weight：3-9 parts of liquor alumini chloridi, sodium hydroxide solution 1-4
Part, 3-6 parts of montmorillonite, 4-8 parts of vermiculite, 3-9 parts of kaolin, 2-5 parts of chitosan, 1-4 parts of antimony oxide, nano magnesia 3-
6 parts, 4-8 parts of chrysotile, 2-8 parts of ceramic powder, 3-6 parts of nanometer silicon carbide, 2-5 parts of octylisothiazolinone, silane coupler
2-8 parts of Z6011.
Preferably, modified toughened dose is prepared by following technique：Sodium hydroxide solution is added in liquor alumini chloridi, is stirred
Mix uniform, be stored at room temperature 10-20d and obtain material a, montmorillonite, vermiculite, kaolin, chitosan, three are then added into material a
Aoxidize two antimony, nano magnesia, chrysotile, ceramic powder and nanometer silicon carbide well mixed, be stored at room temperature 2-6d, then add pungent
Base OIT and silane coupler Z6011 are well mixed, stir 1-3h in 1500-2500r/min rotating speeds, then heat to
100-120 DEG C, 2-5h is dried, is cooled to after room temperature and crushes obtained modified toughened dose.
Preferably, in modified toughened dose of preparation technology, the mass fraction of liquor alumini chloridi is 8-16%, and sodium hydroxide is molten
The mass fraction of liquid is 4-9%.
A kind of medical corrosion-resistant high tenacity 3D printing material of the present invention, its raw material includes ABS resin, SAN resins, suitable
Buna, neoprene, epoxy acrylic resin, polymethyl methacrylate, makrolon, polyolefin elastomer, sulphur, two
Sulfur chloride, chlorinated paraffin, dimethicone, Firebrake ZB, isocyanates, nano-graphite, carbon black, blanc fixe, nanometer hydroxide
Aluminium, polyphosphoric acids aluminium, nano silicon, mica powder, talcum powder, silane coupler KH-560, kodalk, pentaerythrite,
PLA, pla-pcl, odium stearate, neopelex, antioxidant, degasser, dimethicone, anti-corrosive aids,
Modified filler and plasticized modifier.Wherein, anti-corrosive aids are by the way that butyl acrylate and nano tin oxide powder are well mixed,
Then Silane coupling reagent KH-570 is added, stirs, is cooled to room temperature, is subsequently placed in ice-water bath and crushes, it is ultrasonically treated to obtain thing
Expect a；The concentrated sulfuric acid is scattered in distilled water, stir to obtain acid compound aqueous intercalation solution；Montmorillonite is put into calcining furnace
Calcining, cooling is put into hydrochloric acid solution and soaked, and filtering is taken out, and is cleaned drying with clear water, is ground into powder and is then added to acidity
Compound aqueous intercalation solution is well mixed, and is then heated up, and is incubated, is subsequently added into material a, calcium sulfate, silicon nitride, montmorillonite powder, sulphur
Sour barium, antimony trioxide, weathered coal, seawood meal, trbasic zinc phosphate, bentonite, zeolite powder and zirconium oxide are well mixed, surpass in a water bath
Sound-mechanical agitation is disperseed, stratification, removes supernatant liquor, and lower reaction product layer is carried out into suction filtration, and washing is dried under vacuum to
Constant weight, grinds, and sieving obtains anti-corrosive aids, by preparing acid intercalation solution, will.Calcium sulfate, silicon nitride, montmorillonite powder,
The acidity that barium sulfate, antimony trioxide, weathered coal, seawood meal, trbasic zinc phosphate, bentonite, zeolite powder and zirconium oxide are inserted into preparation is inserted
In layer solution, obtained modification anti-corrosive aids are applied in the 3D printing material of the present invention so that 3D printing material of the invention
With excellent antiseptic property.Wherein, modified filler is by under nitrogen protection, by wood fiber powder, bamboo fibre, tapioca starch,
Distilled water and maleic anhydride are well mixed, then heat up, and are incubated, and then add ammonium persulfate and are well mixed, benzene is added after stirring
Ethene is well mixed, and is followed by stirring for, is then heated up, and is extracted, then in vacuum drying oven, is dried to constant weight, be cooled to room temperature, then
Add potassium acetate to be well mixed, vibrate, grind, stand, then freeze-day with constant temperature, grind, wash, drying is subsequently added into hexadecane
Base trimethylammonium bromide, titanate coupling agent and water are well mixed, heat, insulation, and suction filtration is dried, is cooled to room temperature and changed
Property filler, in the 3 3D printing material for applying to the present invention so that 3D printing material of the invention has excellent toughness and anti-
Rotten performance.Wherein.Modified toughened dose, by adding sodium hydroxide solution in liquor alumini chloridi, stirs, and is stored at room temperature
To material a, montmorillonite, vermiculite, kaolin, chitosan, antimony oxide, nano magnesia, fire stons are then added into material a
Cotton, ceramic powder and nanometer silicon carbide are well mixed, are stored at room temperature, and then add octylisothiazolinone and silane coupler
Z6011 is well mixed, stirring, is then heated up, and is dried, and is cooled to after room temperature and is crushed obtained modified toughened dose, applies to the present invention
3D printing material in so that 3D printing material of the invention has excellent toughness.The 3D printing material of the present invention has excellent
Different corrosion-resistant and toughness.
Embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
It is bright, rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
In embodiment, the parts by weight of ABS resin can for 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91
Part, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105
Part, 106 parts, 107 parts, 108 parts, 109 parts, 110 parts, 111 parts, 112 parts, 113 parts, 114 parts, 115 parts, 116 parts, 117 parts,
118 parts, 119 parts, 120 parts, 121 parts, 122 parts, 123 parts, 124 parts, 125 parts；The parts by weight of SAN resins can for 20 parts, 25
Part, 30 parts, 35 parts, 40 parts；The parts by weight of butadiene rubber can for 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13
Part, 14 parts, 15 parts；The parts by weight of neoprene can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；Propylene oxide
The parts by weight of acid resin can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；Polymethylacrylic acid
The parts by weight of methyl esters can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；The parts by weight of makrolon can for 1 part, 1.5 parts, 2 parts, 2.5
Part, 3 parts, 3.5 parts, 4 parts；The parts by weight of polyolefin elastomer can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；
The parts by weight of sulphur can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of sulfur dichloride can be 1
Part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The parts by weight of chlorinated paraffin can be 1
Part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The parts by weight of dimethicone can for 2 parts, 2.5 parts, 3 parts, 3.5 parts,
4 parts；The parts by weight of Firebrake ZB can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The parts by weight of isocyanates can for 3 parts, 3.5 parts, 4
Part, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；The parts by weight of nano-graphite can for 2 parts, 3 parts, 4 parts,
5 parts, 6 parts；The parts by weight of carbon black can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The parts by weight of blanc fixe
It can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；The parts by weight of nano-aluminum hydroxide can be 4
Part, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；The parts by weight of polyphosphoric acids aluminium can for 1 part, 1.5 parts,
2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of nano silicon can for 2 parts, 2.5 parts, 3 parts, 3.5
Part, 4 parts, 4.5 parts, 5 parts；The parts by weight of mica powder can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of talcum powder can
Think 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts；Silane coupler KH-560 parts by weight can for 2 parts, 3 parts, 4 parts, 5
Part, 6 parts；The parts by weight of kodalk can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The parts by weight of pentaerythrite can be with
For 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The parts by weight of PLA can for 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4
Part；The parts by weight of pla-pcl can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6
Part；The parts by weight of odium stearate can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；The parts by weight of neopelex can be 1
Part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The parts by weight of antioxidant can for 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts,
5.5 parts, 6 parts；The parts by weight of degasser can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Dimethicone
Parts by weight can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The parts by weight of anti-corrosive aids can for 3 parts, 4 parts, 5 parts, 6 parts, 7
Part, 8 parts, 9 parts；The parts by weight of modified filler can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The weight of plasticized modifier
Part can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 9 parts.
Embodiment 1
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
105 parts of fat, 30 parts of SAN resins, 10 parts of butadiene rubber, 4.5 parts of neoprene, 6 parts of epoxy acrylic resin, polymethylacrylic acid
4 parts of methyl esters, 2.5 parts of makrolon, 4.5 parts of polyolefin elastomer, 3.5 parts of sulphur, 3.5 parts of sulfur dichloride, chlorinated paraffin 2.5
Part, 3 parts of dimethicone, 3 parts of Firebrake ZB, 5.5 parts of isocyanates, 4 parts of nano-graphite, 4.5 parts of carbon black, 6 parts of blanc fixe, receive
6 parts of aluminium hydroxide of rice, 3 parts of polyphosphoric acids aluminium, 3.5 parts of nano silicon, 4 parts of mica powder, 6 parts of talcum powder, silane coupler
4 parts of KH-560,5 parts of kodalk, 2.5 parts of pentaerythrite, 3 parts of PLA, 3.5 parts of pla-pcl, 4 parts of odium stearate, 12
2.5 parts of sodium alkyl benzene sulfonate, 4.5 parts of antioxidant, 3.5 parts of degasser, 5 parts of dimethicone, 6 parts of anti-corrosive aids, modified filler 5
Part, 6.5 parts of plasticized modifier.
Anti-corrosive aids are prepared by following technique：By weight by 4.5 parts of butyl acrylates and 6 parts of nano-stannic oxides
Powder is well mixed, and then adds 6 parts of Silane coupling reagent KH-570s, is stirred 24h in 42 DEG C, is cooled to room temperature, is subsequently placed in ice
Crushed in water-bath, ultrasonically treated 12min obtains material a；3.5 parts of concentrated sulfuric acids are scattered in 10 parts of distilled water, stirred
The compound aqueous intercalation solution of acidity；4.5 parts of montmorillonites are put into calcining furnace and calcine 3h at 800 DEG C, cools down, is put into 5 parts of hydrochloric acid
3h is soaked in solution, filtering is taken out, and drying is cleaned with clear water, be ground into 250 mesh powder and be then added to acid compound intercalation water
Solution is well mixed, and then heats to 90 DEG C, is incubated 2h, be subsequently added into material a, 4 parts of calcium sulfate, 2.5 parts of silicon nitrides, 3.5 parts
Montmorillonite powder, 4.5 parts of barium sulfate, 3 parts of antimony trioxides, 4.5 parts of weathered coals, 6 portions of seawood meals, 5 parts of trbasic zinc phosphates, 4.5 parts of bentonites,
2.5 parts of zeolite powders and 5 parts of zirconium oxides are well mixed, and ultrasound-mechanical agitation disperses 3h in 50 DEG C of water-baths, and stratification is removed
Supernatant liquor, suction filtration is carried out by lower reaction product layer, is washed, 800 DEG C are dried under vacuum to constant weight, and grinding is crossed 200 mesh sieves, produced
To anti-corrosive aids.
Modified filler is prepared by following technique：Under nitrogen protection, by weight by 4.5 parts of wood fiber powders, 3.5
Part bamboo fibre, 6 parts of tapioca starch, distilled water and 4.5 parts of maleic anhydrides are well mixed, and are then heated to 85 DEG C, are incubated 20min, so
Add 3.5 parts of ammonium persulfates afterwards to be well mixed, adding 2.5 parts of styrene after stirring 10min is well mixed, then in 1050r/
Min rotating speeds stir 60min, then heat to 90 DEG C, extract 45h, then in vacuum drying oven, 70 DEG C dry to constant weight, and are cooled to
Room temperature, then adds 4.5 parts of potassium acetates and is well mixed, vibrate 4min, grind 20min, stand 23h, then dry in 70 DEG C of constant temperature
Dry 24h, grinds, and washes, drying, is subsequently added into 6 parts of cetyl trimethylammonium bromides, 4 parts of titanate coupling agents and water mixing
Uniformly, 85 DEG C are heated to, 30min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Modified toughened dose is prepared by following technique：By weight in the liquor alumini chloridi that 6 parts of mass fractions are 12%
The sodium hydroxide solution that middle 2.5 parts of mass fractions of addition are 6.5%, stirs, is stored at room temperature 15d and obtains material a, Ran Houxiang
Added in material a 4.5 parts of montmorillonites, 6 parts of vermiculites, 6 parts of kaolin, 3.5 parts of chitosans, 2.5 parts of antimony oxides, 4.5 parts receive
Rice magnesia, 6 parts of chrysotiles, 5 parts of ceramic powders and 4.5 parts of nanometer silicon carbides are well mixed, and are stored at room temperature 4d, are then added 3.5
Part octylisothiazolinone and 5 parts of silane coupler Z6011 are well mixed, and are stirred 2h in 2000r/min rotating speeds, are then heated to
110 DEG C, 3.5h is dried, is cooled to after room temperature and crushes obtained modified toughened dose.
Embodiment 2
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
85 parts of fat, 40 parts of SAN resins, 5 parts of butadiene rubber, 6 parts of neoprene, 4 parts of epoxy acrylic resin, polymethyl methacrylate
6 parts, 1 part of makrolon, 6 parts of polyolefin elastomer, 2 parts of sulphur, 6 parts of sulfur dichloride, 1 part of chlorinated paraffin, dimethicone 4
Part, 1 part of Firebrake ZB, 8 parts of isocyanates, 2 parts of nano-graphite, 6 parts of carbon black, 4 parts of blanc fixe, 8 parts of nano-aluminum hydroxide, poly
1 part of aluminum phosphate, 5 parts of nano silicon, 3 parts of mica powder, 9 parts of talcum powder, 2 parts of silane coupler KH-560, kodalk 8
Part, 1 part of pentaerythrite, 4 parts of PLA, 1 part of pla-pcl, 6 parts of odium stearate, 1 part of neopelex, antioxidant 6
Part, 2 parts of degasser, 6 parts of dimethicone, 3 parts of anti-corrosive aids, 8 parts of modified filler, 4 parts of plasticized modifier.
Anti-corrosive aids are prepared by following technique：By weight by 3 parts of butyl acrylates and 8 parts of nanometer titanium dioxide glass puttys
Body is well mixed, and then adds 3 parts of Silane coupling reagent KH-570s, is stirred 20h in 46 DEG C, is cooled to room temperature, is subsequently placed in frozen water
Crushed in bath, ultrasonically treated 14min obtains material a；2 parts of concentrated sulfuric acids are scattered in 15 parts of distilled water, stir acid
Compound aqueous intercalation solution；3 parts of montmorillonites are put into calcining furnace and calcine 1h at 850 DEG C, cools down, is put into 8 parts of hydrochloric acid solutions
2h is soaked, filtering is taken out, and drying is cleaned with clear water, be ground into 350 mesh powder and be then added to acid compound aqueous intercalation solution and mix
Close uniform, then heat to 85 DEG C, be incubated 3h, be subsequently added into material a, 3 parts of calcium sulfate, 4 parts of silicon nitrides, 2 parts of montmorillonite powders, 6
Part barium sulfate, 1 part of antimony trioxide, 6 parts of weathered coals, 4 portions of seawood meals, 8 parts of trbasic zinc phosphates, 3 parts of bentonites, 4 parts of zeolite powders and 2 parts of oxygen
Change zirconium to be well mixed, ultrasound-mechanical agitation disperses 2h in 55 DEG C of water-baths, stratification removes supernatant liquor, lower floor is reacted
Product carries out suction filtration, washs, 850 DEG C are dried under vacuum to constant weight, and grinding crosses 150 mesh sieves, that is, obtains anti-corrosive aids.
Modified filler is prepared by following technique：Under nitrogen protection, by weight by 3 parts of wood fiber powders, 5 portions of bamboos
Fiber, 4 parts of tapioca starch, distilled water and 6 parts of maleic anhydrides are well mixed, and are then heated to 80 DEG C, are incubated 30min, then add 2
Part ammonium persulfate is well mixed, and adding 1 part of styrene after stirring 15min is well mixed, then in the stirring of 1250r/min rotating speeds
50min, then heats to 95 DEG C, extracts 40h, then in vacuum drying oven, 75 DEG C dry to constant weight, and are cooled to room temperature, Ran Houjia
Enter 3 parts of potassium acetates to be well mixed, vibrate 5min, grind 10min, stand 26h, then in 60 DEG C of freeze-day with constant temperature 28h, grinding, water
Wash, dry, be subsequently added into 4 parts of cetyl trimethylammonium bromides, 6 parts of titanate coupling agents and water and be well mixed, be heated to 80
DEG C, 40min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Modified toughened dose is prepared by following technique：By weight in the liquor alumini chloridi that 3 parts of mass fractions are 16%
The sodium hydroxide solution that middle 1 part of mass fraction of addition is 9%, stirs, is stored at room temperature 10d and obtains material a, then to material
Added in a 6 parts of montmorillonites, 4 parts of vermiculites, 9 parts of kaolin, 2 parts of chitosans, 4 parts of antimony oxides, 3 parts of nano magnesias, 8 parts
Chrysotile, 2 parts of ceramic powders and 6 parts of nanometer silicon carbides are well mixed, and are stored at room temperature 2d, are then added 5 parts of octylisothiazolinones
It is well mixed with 2 parts of silane coupler Z6011,1h is stirred in 2500r/min rotating speeds, 120 DEG C are then heated to, 2h is dried, it is cold
But it is made modified toughened dose to crushing after room temperature.
Embodiment 3
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
125 parts of fat, 20 parts of SAN resins, 15 parts of butadiene rubber, 3 parts of neoprene, 8 parts of epoxy acrylic resin, poly-methyl methacrylate
2 parts of ester, 4 parts of makrolon, 3 parts of polyolefin elastomer, 5 parts of sulphur, 1 part of sulfur dichloride, 4 parts of chlorinated paraffin, dimethicone 2
Part, 5 parts of Firebrake ZB, 3 parts of isocyanates, 6 parts of nano-graphite, 3 parts of carbon black, 8 parts of blanc fixe, 4 parts of nano-aluminum hydroxide, poly
5 parts of aluminum phosphate, 2 parts of nano silicon, 5 parts of mica powder, 3 parts of talcum powder, 6 parts of silane coupler KH-560, kodalk 2
Part, 4 parts of pentaerythrite, 2 parts of PLA, 6 parts of pla-pcl, 2 parts of odium stearate, 4 parts of neopelex, antioxidant 3
Part, 5 parts of degasser, 4 parts of dimethicone, 9 parts of anti-corrosive aids, 2 parts of modified filler, 9 parts of plasticized modifier.
Anti-corrosive aids are prepared by following technique：By weight by 6 parts of butyl acrylates and 4 parts of nanometer titanium dioxide glass puttys
Body is well mixed, and then adds 9 parts of Silane coupling reagent KH-570s, is stirred 28h in 38 DEG C, is cooled to room temperature, is subsequently placed in frozen water
Crushed in bath, ultrasonically treated 10min obtains material a；5 parts of concentrated sulfuric acids are scattered in 5 parts of distilled water, stir acid multiple
Close aqueous intercalation solution；6 parts of montmorillonites are put into calcining furnace and calcine 5h at 750 DEG C, are cooled down, is put into 2 parts of hydrochloric acid solutions and soaks
4h is steeped, filtering is taken out, and drying is cleaned with clear water, be ground into 150 mesh powder and be then added to acid compound aqueous intercalation solution mixing
Uniformly, then heat to 95 DEG C, be incubated 1h, be subsequently added into material a, 5 parts of calcium sulfate, 1 part of silicon nitride, 5 parts of montmorillonite powders, 3 parts
Barium sulfate, 5 parts of antimony trioxides, 3 parts of weathered coals, 8 portions of seawood meals, 2 parts of trbasic zinc phosphates, 6 parts of bentonites, 1 part of zeolite powder and 8 parts of oxidations
Zirconium is well mixed, and ultrasound-mechanical agitation disperses 4h in 45 DEG C of water-baths, and stratification removes supernatant liquor, lower floor is reacted and produced
Thing carries out suction filtration, washs, 750 DEG C are dried under vacuum to constant weight, and grinding crosses 250 mesh sieves, that is, obtains anti-corrosive aids.
Modified filler is prepared by following technique：Under nitrogen protection, by weight by 6 parts of wood fiber powders, 2 portions of bamboos
Fiber, 8 parts of tapioca starch, distilled water and 3 parts of maleic anhydrides are well mixed, and are then heated to 90 DEG C, are incubated 10min, then add 5
Part ammonium persulfate is well mixed, and adding 4 parts of styrene after stirring 5min is well mixed, then in the stirring of 850r/min rotating speeds
70min, then heats to 85 DEG C, extracts 50h, then in vacuum drying oven, 65 DEG C dry to constant weight, and are cooled to room temperature, Ran Houjia
Enter 6 parts of potassium acetates to be well mixed, vibrate 3min, grind 30min, stand 20h, then in 80 DEG C of freeze-day with constant temperature 20h, grinding, water
Wash, dry, be subsequently added into 8 parts of cetyl trimethylammonium bromides, 2 parts of titanate coupling agents and water and be well mixed, be heated to 90
DEG C, 20min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Modified toughened dose is prepared by following technique：By weight in 9 parts of mass fractions in 8% liquor alumini chloridi
The sodium hydroxide solution that 4 parts of mass fractions of addition are 4%, stirs, is stored at room temperature 20d and obtains material a, then to material a
Middle addition 3 parts of montmorillonites, 8 parts of vermiculites, 3 parts of kaolin, 5 parts of chitosans, 1 part of antimony oxide, 6 parts of nano magnesias, 4 parts of temperature
Asbestos, 8 parts of ceramic powders and 3 parts of nanometer silicon carbides are well mixed, and are stored at room temperature 6d, are then added 2 parts of octylisothiazolinones and 8
Part silane coupler Z6011 is well mixed, and 3h is stirred in 1500r/min rotating speeds, then heats to 100 DEG C, is dried 5h, is cooled to
Crushed after room temperature and be made modified toughened dose.
Embodiment 4
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
88 parts of fat, 35 parts of SAN resins, 8 parts of butadiene rubber, 5 parts of neoprene, 5 parts of epoxy acrylic resin, polymethyl methacrylate
5 parts, 2 parts of makrolon, 5 parts of polyolefin elastomer, 3 parts of sulphur, 5 parts of sulfur dichloride, 2 parts of chlorinated paraffin, dimethicone 3.5
Part, 2 parts of Firebrake ZB, 7 parts of isocyanates, 3 parts of nano-graphite, 5 parts of carbon black, 5 parts of blanc fixe, 7 parts of nano-aluminum hydroxide, poly
2 parts of aluminum phosphate, 4 parts of nano silicon, 3.5 parts of mica powder, 8 parts of talcum powder, KH-5603 parts of silane coupler, kodalk 7
Part, 2 parts of pentaerythrite, 3.5 parts of PLA, 2 parts of pla-pcl, 5 parts of odium stearate, 2 parts of neopelex, antioxidant
5 parts, 3 parts of degasser, 5.5 parts of dimethicone, 4 parts of anti-corrosive aids, 7 parts of modified filler, 5 parts of plasticized modifier.
Anti-corrosive aids are prepared by following technique：By weight by 4 parts of butyl acrylates and 7 parts of nanometer titanium dioxide glass puttys
Body is well mixed, and then adds 4 parts of Silane coupling reagent KH-570s, is stirred 22h in 45 DEG C, is cooled to room temperature, is subsequently placed in frozen water
Crushed in bath, ultrasonically treated 13min obtains material a；3 parts of concentrated sulfuric acids are scattered in 12 parts of distilled water, stir acid
Compound aqueous intercalation solution；4 parts of montmorillonites are put into calcining furnace and calcine 2h at 820 DEG C, cools down, is put into 7 parts of hydrochloric acid solutions
2.5h is soaked, filtering is taken out, and drying is cleaned with clear water, be ground into 320 mesh powder and be then added to acid compound aqueous intercalation solution
It is well mixed, 88 DEG C are then heated to, 2.5h is incubated, material a, 3.5 parts of calcium sulfate, 3 parts of silicon nitrides, 3 parts of illiteracies is subsequently added into and takes off
Stone flour, 5 parts of barium sulfate, 2 parts of antimony trioxides, 5 parts of weathered coals, 5 parts of seawood meals, 7 parts of trbasic zinc phosphates, 4 parts of bentonites, 3 parts of zeolite powders
Well mixed with 3 parts of zirconium oxides, ultrasound-mechanical agitation disperses 2.5h in 52 DEG C of water-baths, and stratification removes supernatant liquor,
Lower reaction product layer is subjected to suction filtration, washed, 820 DEG C are dried under vacuum to constant weight, grinding crosses 180 mesh sieves, that is, obtains anti-corrosion and help
Agent.
Modified filler is prepared by following technique：Under nitrogen protection, by weight by 4 parts of wood fiber powders, 4 portions of bamboos
Fiber, 5 parts of tapioca starch, distilled water and 5 parts of maleic anhydrides are well mixed, and are then heated to 82 DEG C, are incubated 25min, then add 3
Part ammonium persulfate is well mixed, and adding 2 parts of styrene after stirring 12min is well mixed, then in the stirring of 1220r/min rotating speeds
55min, then heats to 92 DEG C, extracts 42h, then in vacuum drying oven, 72 DEG C dry to constant weight, and are cooled to room temperature, Ran Houjia
Enter 4 parts of potassium acetates to be well mixed, vibrate 4.5min, grind 15min, stand 25h, then in 65 DEG C of freeze-day with constant temperature 26h, grinding,
Washing, drying is subsequently added into 5 parts of cetyl trimethylammonium bromides, 5 parts of titanate coupling agents and water and is well mixed, is heated to
82 DEG C, 35min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Modified toughened dose is prepared by following technique：By weight in the liquor alumini chloridi that 4 parts of mass fractions are 15%
The sodium hydroxide solution that middle 2 parts of mass fractions of addition are 8%, stirs, is stored at room temperature 12d and obtains material a, then to material
Added in a 5 parts of montmorillonites, 5 parts of vermiculites, 8 parts of kaolin, 3 parts of chitosans, 3 parts of antimony oxides, 4 parts of nano magnesias, 7 parts
Chrysotile, 3 parts of ceramic powders and 5 parts of nanometer silicon carbides are well mixed, and are stored at room temperature 3d, are then added 4 parts of octylisothiazolinones
It is well mixed with 3 parts of silane coupler Z6011,1.5h is stirred in 2200r/min rotating speeds, 115 DEG C are then heated to, 3h is dried,
It is cooled to crush after room temperature and is made modified toughened dose.
Embodiment 5
The medical corrosion-resistant high tenacity 3D printing material of one kind proposed by the present invention, its raw material includes by weight：ABS trees
122 parts of fat, 25 parts of SAN resins, 12 parts of butadiene rubber, 4 parts of neoprene, 7 parts of epoxy acrylic resin, poly-methyl methacrylate
3 parts of ester, 3 parts of makrolon, 4 parts of polyolefin elastomer, 4 parts of sulphur, 2 parts of sulfur dichloride, 3 parts of chlorinated paraffin, dimethicone
2.5 parts, 4 parts of Firebrake ZB, 4 parts of isocyanates, 5 parts of nano-graphite, 4 parts of carbon black, 7 parts of blanc fixe, 5 parts of nano-aluminum hydroxide,
4 parts of polyphosphoric acids aluminium, 3 parts of nano silicon, 4.5 parts of mica powder, 4 parts of talcum powder, KH-5605 parts of silane coupler, inclined boron
Sour 3 parts of sodium, 3 parts of pentaerythrite, 2.5 parts of PLA, 5 parts of pla-pcl, 3 parts of odium stearate, 3 parts of neopelex,
4 parts of antioxidant, 4 parts of degasser, 4.5 parts of dimethicone, 8 parts of anti-corrosive aids, 3 parts of modified filler, 8 parts of plasticized modifier.
Anti-corrosive aids are prepared by following technique：By weight by 5 parts of butyl acrylates and 5 parts of nanometer titanium dioxide glass puttys
Body is well mixed, and then adds 8 parts of Silane coupling reagent KH-570s, is stirred 26h in 39 DEG C, is cooled to room temperature, is subsequently placed in frozen water
Crushed in bath, ultrasonically treated 11min obtains material a；4 parts of concentrated sulfuric acids are scattered in 8 parts of distilled water, stir acid multiple
Close aqueous intercalation solution；5 parts of montmorillonites are put into calcining furnace and calcine 4h at 780 DEG C, are cooled down, is put into 3 parts of hydrochloric acid solutions and soaks
3.5h is steeped, filtering is taken out, and drying is cleaned with clear water, be ground into 180 mesh powder and be then added to acid compound aqueous intercalation solution and mix
Close uniform, then heat to 92 DEG C, be incubated 1.5h, be subsequently added into material a, 4.5 parts of calcium sulfate, 2 parts of silicon nitrides, 4 parts of montmorillonites
Powder, 4 parts of barium sulfate, 4 parts of antimony trioxides, 4 parts of weathered coals, 7 parts of seawood meals, 3 parts of trbasic zinc phosphates, 5 parts of bentonites, 2 parts of zeolite powders and 7
Part zirconium oxide is well mixed, and ultrasound-mechanical agitation disperses 3.5h in 48 DEG C of water-baths, and stratification removes supernatant liquor, by under
Reaction product layer carries out suction filtration, washs, 780 DEG C are dried under vacuum to constant weight, and grinding crosses 220 mesh sieves, that is, obtains anti-corrosive aids.
Modified filler is prepared by following technique：Under nitrogen protection, by weight by 5 parts of wood fiber powders, 3 portions of bamboos
Fiber, 7 parts of tapioca starch, distilled water and 4 parts of maleic anhydrides are well mixed, and are then heated to 88 DEG C, are incubated 15min, then add 4
Part ammonium persulfate is well mixed, and adding 3 parts of styrene after stirring 8min is well mixed, then in the stirring of 880r/min rotating speeds
65min, then heats to 88 DEG C, extracts 48h, then in vacuum drying oven, 68 DEG C dry to constant weight, and are cooled to room temperature, Ran Houjia
Enter 5 parts of potassium acetates to be well mixed, vibrate 3.5min, grind 25min, stand 21h, then in 75 DEG C of freeze-day with constant temperature 22h, grinding,
Washing, drying is subsequently added into 7 parts of cetyl trimethylammonium bromides, 3 parts of titanate coupling agents and water and is well mixed, is heated to
88 DEG C, 25min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
Modified toughened dose is prepared by following technique：By weight in 8 parts of mass fractions in 9% liquor alumini chloridi
The sodium hydroxide solution that 3 parts of mass fractions of addition are 5%, stirs, is stored at room temperature 18d and obtains material a, then to material a
Middle addition 4 parts of montmorillonites, 7 parts of vermiculites, 4 parts of kaolin, 4 parts of chitosans, 2 parts of antimony oxides, 5 parts of nano magnesias, 5 parts of temperature
Asbestos, 7 parts of ceramic powders and 4 parts of nanometer silicon carbides are well mixed, and are stored at room temperature 5d, are then added 3 parts of octylisothiazolinones and 7
Part silane coupler Z6011 is well mixed, and 2.5h is stirred in 1800r/min rotating speeds, then heats to 105 DEG C, dries 4h, cooling
Crushed after to room temperature and be made modified toughened dose.
By the medical corrosion-resistant high tenacity 3D printing material application in embodiment 1-5 into actual 3D printing production, institute
The performance of obtained product is detected that obtained data are as shown in table 1.
Table 1：
As shown in Table 1, the medical corrosion-resistant high tenacity 3D printing material in embodiment 1- embodiments 5 has excellent tough
Property and decay resistance.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (8)
1. a kind of medical corrosion-resistant high tenacity 3D printing material, it is characterised in that its raw material includes by weight：ABS resin
85-125 parts, 20-40 parts of SAN resins, 5-15 parts of butadiene rubber, 3-6 parts of neoprene, 4-8 parts of epoxy acrylic resin, poly- first
2-6 parts of base methyl acrylate, 1-4 parts of makrolon, 3-6 parts of polyolefin elastomer, 2-5 parts of sulphur, 1-6 parts of sulfur dichloride, chlorine
1-4 parts of fossil waxes, 2-4 parts of dimethicone, 1-5 parts of Firebrake ZB, 3-8 parts of isocyanates, 2-6 parts of nano-graphite, carbon black 3-6
Part, 4-8 parts of blanc fixe, 4-8 parts of nano-aluminum hydroxide, 1-5 parts of polyphosphoric acids aluminium, 2-5 parts of nano silicon, mica powder 3-
5 parts, 3-9 parts of talcum powder, 2-6 parts of silane coupler KH-560,2-8 parts of kodalk, 1-4 parts of pentaerythrite, PLA 2-4
Part, 1-6 parts of pla-pcl, 2-6 parts of odium stearate, 1-4 parts of neopelex, 3-6 parts of antioxidant, 2-5 parts of degasser,
4-6 parts of dimethicone, 3-9 parts of anti-corrosive aids, 2-8 parts of modified filler, 4-9 parts of plasticized modifier.
2. medical corrosion-resistant high tenacity 3D printing material according to claim 1, it is characterised in that the original of anti-corrosive aids
Material includes by weight：3-6 parts of butyl acrylate, 4-8 parts of nano tin oxide powder, 3-9 parts of Silane coupling reagent KH-570,
2-5 parts of the concentrated sulfuric acid, 5-15 parts of distilled water, 3-6 parts of montmorillonite, 2-8 parts of hydrochloric acid solution, 3-5 parts of calcium sulfate, 1-4 parts of silicon nitride, illiteracy
It is de- 2-5 parts of stone flour, 3-6 parts of barium sulfate, 1-5 parts of antimony trioxide, 3-6 parts of weathered coal, 4-8 parts of seawood meal, 2-8 parts of trbasic zinc phosphate, swollen
Moisten 3-6 parts of soil, 1-4 parts of zeolite powder, 2-8 parts of zirconium oxide.
3. medical corrosion-resistant high tenacity 3D printing material according to claim 1 or 2, it is characterised in that anti-corrosive aids
Prepared by following technique：Butyl acrylate and nano tin oxide powder are well mixed, silane coupler is then added
KH-570, stirs 20-28h in 38-46 DEG C, is cooled to room temperature, is subsequently placed in ice-water bath and crushes, ultrasonically treated 10-14min is obtained
To material a；The concentrated sulfuric acid is scattered in distilled water, stir to obtain acid compound aqueous intercalation solution；Montmorillonite is put into calcining
1-5h is calcined at 750-850 DEG C in stove, is cooled down, is put into hydrochloric acid solution and soaks 2-4h, filtering is taken out, is cleaned and dried with clear water
It is dry, it is ground into 150-350 mesh powder and is then added to acid compound aqueous intercalation solution and be well mixed, then heats to 85-95 DEG C,
Be incubated 1-3h, be subsequently added into material a, calcium sulfate, silicon nitride, montmorillonite powder, barium sulfate, antimony trioxide, weathered coal, seawood meal,
Trbasic zinc phosphate, bentonite, zeolite powder and zirconium oxide are well mixed, and ultrasound-mechanical agitation disperses 2-4h in 45-55 DEG C of water-bath, quiet
Layering is put, supernatant liquor is removed, lower reaction product layer is subjected to suction filtration, is washed, 750-850 DEG C is dried under vacuum to constant weight, grinding,
150-250 mesh sieves are crossed, that is, obtain anti-corrosive aids.
4. the medical corrosion-resistant high tenacity 3D printing material according to claim any one of 1-3, it is characterised in that modified
The raw material of filler includes by weight：3-6 parts of wood fiber powder, 2-5 parts of bamboo fibre, 4-8 parts of tapioca starch, 3-6 parts of maleic anhydride,
2-5 parts of ammonium persulfate, 1-4 parts of styrene, 3-6 parts of potassium acetate, 4-8 parts of cetyl trimethylammonium bromide, titanate coupling agent
2-6 parts.
5. the medical corrosion-resistant high tenacity 3D printing material according to claim any one of 1-4, it is characterised in that modified
Filler is prepared by following technique：Under nitrogen protection, by wood fiber powder, bamboo fibre, tapioca starch, distilled water and maleic acid
Acid anhydride is well mixed, and then heats to 80-90 DEG C, is incubated 10-30min, is then added ammonium persulfate and is well mixed, stirs 5-
Styrene is added after 15min to be well mixed, and is then stirred 50-70min in 850-1250r/min rotating speeds, is then heated to 85-95
DEG C, 40-50h is extracted, then in vacuum drying oven, 65-75 DEG C dries to constant weight, and is cooled to room temperature, then add potassium acetate mixing
Uniformly, 3-5min is vibrated, 10-30min is ground, 20-26h is stood, then in 60-80 DEG C of freeze-day with constant temperature 20-28h, grinding, water
Wash, dry, be subsequently added into cetyl trimethylammonium bromide, titanate coupling agent and water and be well mixed, be heated to 80-90 DEG C,
20-40min is incubated, suction filtration is dried, is cooled to room temperature and obtains modified filler.
6. the medical corrosion-resistant high tenacity 3D printing material according to claim any one of 1-5, it is characterised in that modified
The raw material of toughener includes by weight：3-9 parts of liquor alumini chloridi, 1-4 parts of sodium hydroxide solution, 3-6 parts of montmorillonite, vermiculite 4-
8 parts, 3-9 parts of kaolin, 2-5 parts of chitosan, 1-4 parts of antimony oxide, 3-6 parts of nano magnesia, 4-8 parts of chrysotile, ceramics
2-8 parts of powder, 3-6 parts of nanometer silicon carbide, 2-5 parts of octylisothiazolinone, 2-8 parts of silane coupler Z6011.
7. the medical corrosion-resistant high tenacity 3D printing material according to claim any one of 1-6, it is characterised in that modified
Toughener is prepared by following technique：Sodium hydroxide solution is added in liquor alumini chloridi, is stirred, 10- is stored at room temperature
20d obtains material a, montmorillonite is then added into material a, vermiculite, kaolin, chitosan, antimony oxide, nano oxidized
Magnesium, chrysotile, ceramic powder and nanometer silicon carbide are well mixed, are stored at room temperature 2-6d, then add octylisothiazolinone and silicon
Alkane coupling agent Z6011 is well mixed, and 1-3h is stirred in 1500-2500r/min rotating speeds, then heats to 100-120 DEG C, dries 2-
5h, is cooled to after room temperature and crushes obtained modified toughened dose.
8. the medical corrosion-resistant high tenacity 3D printing material according to claim any one of 1-7, it is characterised in that modified
In the preparation technology of toughener, the mass fraction of liquor alumini chloridi is 8-16%, and the mass fraction of sodium hydroxide solution is 4-
9%.
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Application publication date: 20170901 |