CN107698926A

CN107698926A - A kind of wear-resisting 3D printing material of building water-proof

Info

Publication number: CN107698926A
Application number: CN201710829045.3A
Authority: CN
Inventors: 吕月林
Original assignee: Wuhu Woods One Electronic Science And Technology Co Ltd
Current assignee: Wuhu Woods One Electronic Science And Technology Co Ltd
Priority date: 2017-09-14
Filing date: 2017-09-14
Publication date: 2018-02-16

Abstract

The invention discloses a kind of wear-resisting 3D printing material of building water-proof, its raw material includes ABS resin, Lauxite, polypropylene, makrolon, end carboxyl nitrile rubber, phenolic resin, trimethyl phosphate, glass fibre, carbon fiber, nylon, multi-walled carbon nanotube, nano imvite, carbon black, superfine silicon dioxide, polytetrafluoroethylene (PTFE), ALS, methyl acrylate, n-propyl, double Lauryl Alcohol esters, silane coupler KH 560, benzoyl peroxide, water-repellent modified auxiliary agent and wear-resisting modified filler.The 3D printing material for building of the present invention has excellent waterproof and anti-wear performance.

Description

A kind of wear-resisting 3D printing material of building water-proof

Technical field

The present invention relates to the technical field of 3D printing material, more particularly to a kind of wear-resisting 3D printing material of building water-proof.

Background technology

3D printing is according to designed 3D models, successively increases material by 3D printing equipment to manufacture three-dimensional objects For this successively stack shaping technologies of technology also referred to as increasing material manufacturing, 3D printing combines digital modeling techniques, Electromechanical Control skill The cutting edge technology of the numerous areas such as art, information technology, material science and chemistry, it is one kind of rapid shaping technique, be described as " the The core technology of the industrial revolution three times ".Material is the material base of 3D printing, and the bottleneck of restricting current 3D printing development, Here the problem of briefly introducing the current situation of current 3D printing material and existing.3D printing technique has penetrated into all trades and professions In, the needs of when the waterproof and anti-wear performance of 3D printing material for building can not meet actual use, so needing exploitation one The wear-resisting 3D printing material of building water-proof is planted 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 wear-resisting 3D printing material of building water-proof Material, has excellent waterproof and anti-wear performance.

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 80-120 parts, Lauxite 30-50 parts, -35 parts of polipropene 25, makrolon 18-36 parts, end carboxyl nitrile rubber 30-60 parts, Phenolic resin 2-5 parts, trimethyl phosphate 4-8 parts, glass fibre 4-6 parts, carbon fiber 2-8 parts, nylon 4-9 parts, multi-wall carbon nano-tube Pipe 3-5 parts, nano imvite 1-3 parts, carbon black 2-5 parts, superfine silicon dioxide 1-4 parts, polytetrafluoroethylene (PTFE) 2-6 parts, pi-allyl sulphur Sour sodium 2-5 parts, methyl acrylate 2-8 parts, n-propyl 1-6 parts, double Lauryl Alcohol ester 3-8 parts, silane coupler KH- 560 2-6 parts, benzoyl peroxide 1-8 parts, water-repellent modified auxiliary agent 5-15 parts, wear-resisting modified filler 6-12 parts.

Preferably, the raw material of water-repellent modified auxiliary agent includes by weight：Bentonite 5-15 parts, blanc fixe 3-6 parts, nitrification Cotton 2-5 parts, zinc oxide 1-4 parts, mica powder 3-5 parts, zeolite powder 2-5 parts, concentrated sulfuric acid 1-9 parts, carbamate 2-5 parts, propylene Isopropyl propionate 1-5 parts, white carbon 3-6 parts, tetraethyl orthosilicate 2-5 parts, wood fibre 1-4 parts, Silane coupling reagent KH-570 3- 6 parts, polyvinylpyrrolidone 4-8 parts.

Preferably, water-repellent modified auxiliary agent is prepared by following technique：By bentonite, blanc fixe, nitrocotton, oxidation Zinc, mica powder, zeolite powder and the concentrated sulfuric acid are well mixed, and are heated up, and insulation, are then stirred, and are filtered, and are washed to neutrality, are filtered, dry Dry, grinding, sieving obtains material a；Then by material a, carbamate, isopropyl acrylate, white carbon, tetraethyl orthosilicate It is well mixed with wood fibre, ultrasound-mechanical agitation is distributed to material b in a water bath, is then added into material b silane coupled Agent KH-570 and polyvinylpyrrolidone are well mixed, and are heated up, and insulation, nitrogen are led to during insulation, finally by reaction product Pour out, add distilled water, stir, stratification, remove supernatant liquor, lower reaction product layer is filtered, wash, very Sky is dried to constant weight, is ground, and sieving, that is, obtains water-repellent modified auxiliary agent.

Preferably, water-repellent modified auxiliary agent is prepared by following technique：By bentonite, blanc fixe, nitrocotton, oxidation Zinc, mica powder, zeolite powder and the concentrated sulfuric acid are well mixed, and are warming up to 80-90 DEG C, 5-15min are incubated, then in 1500-2500r/ Min rotating speeds stir 2-4h, filtering, wash to neutrality, filter, dry, and grinding, cross 150-250 mesh sieves and obtain material a；Then will Material a, carbamate, isopropyl acrylate, white carbon, tetraethyl orthosilicate and wood fibre are well mixed, at 45-55 DEG C The scattered 2-4h of ultrasound-mechanical agitation obtains material b in water-bath, and Silane coupling reagent KH-570 and poly- second are then added into material b Alkene pyrrolidone is well mixed, and is warming up to 75-85 DEG C, is incubated 5-7h, and nitrogen is led to during insulation, finally falls reaction product Go out, add distilled water, stir, stratification, remove supernatant liquor, lower reaction product layer is filtered, wash, 750- 850 DEG C are dried under vacuum to constant weight, grinding, cross 150-250 mesh sieves, that is, obtain water-repellent modified auxiliary agent.

Preferably, the original of wear-resisting modified filler includes by weight：Phenolic resin 4-8 parts, 4- hydroxy phenyls Malaysia acyl Imines 3-6 parts, silica fibre 2-5 parts, melamine 1-8 parts, silane resin acceptor kh-550 4-6 parts, tapioca starch 3-6 parts, kaolin 2-5 parts, calcium carbonate 1-5 parts, nanometer silicon carbide 3-6 parts, Nano diamond 1-5 parts, attapulgite 4-8 parts.

Preferably, wear-resisting modified filler is prepared by following technique：Phenolic resin and deionized water are mixed, Ran Housheng Temperature, insulation, pH is adjusted, 4- hydroxyphenyl-maleimides is subsequently added into and is well mixed, heated up, insulation, adjusted pH, be subsequently added into Silica fibre and melamine are well mixed, and are cooled, and insulation, continue to cool down, and are discharged, are cooled to room temperature and obtain material A；Silane is even Connection agent KH-550 and distilled water are well mixed, and are then placed in water-bath and are heated, are subsequently added into material A, tapioca starch, kaolin, carbon Sour calcium, nanometer silicon carbide, Nano diamond and attapulgite are well mixed, and ultrasonic disperse, then adjust pH, are then placed in water-bath Middle heating, separation of solid and liquid is then carried out, by the solid after separation with water washing is distilled, then it is de- to carry out distillation for addition n-butanol Water, then the powder after dehydration is put into baking oven and dried, room temperature is cooled to and obtains wear-resisting modified filler.

Preferably, wear-resisting modified filler is prepared by following technique：Phenolic resin and deionized water are mixed, Ran Housheng Temperature is incubated 10-20min to 90-95 DEG C, adjusts pH to 2-3, is subsequently added into 4- hydroxyphenyl-maleimides and is well mixed, and rises Temperature is incubated 60-80min to 95-100 DEG C, adjusts pH to 7-8, is subsequently added into silica fibre and melamine is well mixed, be cooled to 80-85 DEG C, 40-60min is incubated, 50-60 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By silane coupler KH-550 and distilled water are well mixed, and are then placed in water-bath and are heated 25-35min, are subsequently added into material A, tapioca starch, kaolinite Soil, calcium carbonate, nanometer silicon carbide, Nano diamond and attapulgite are well mixed, and ultrasonic disperse 10-20min, then adjust pH To 2.5-3.5, it is then placed in water-bath and heats 25-35min, then carry out separation of solid and liquid, by the solid distilled water after separation Washing 2-4 times, then add n-butanol and carry out distillation dehydration, then the powder after dehydration is put into 100-120 DEG C of baking oven and done Dry 1-3h, it is cooled to room temperature and obtains wear-resisting modified filler.

A kind of wear-resisting 3D printing material of building water-proof of the present invention, its raw material include ABS resin, Lauxite, poly- third Alkene, makrolon, end carboxyl nitrile rubber, phenolic resin, trimethyl phosphate, glass fibre, carbon fiber, nylon, more wall carbon are received Mitron, nano imvite, carbon black, superfine silicon dioxide, polytetrafluoroethylene (PTFE), ALS, methyl acrylate, acrylic acid are just Propyl ester, double Lauryl Alcohol esters, silane coupler KH-560, benzoyl peroxide, water-repellent modified auxiliary agent and wear-resisting modified filler.Its In using ABS resin, Lauxite, polypropylene, makrolon, end carboxyl nitrile rubber and phenolic resin as base-material, with tricresyl phosphate Methyl esters, glass fibre, carbon fiber, nylon, multi-walled carbon nanotube, nano imvite, carbon black, superfine silicon dioxide, polytetrafluoroethyl-ne Alkene, ALS, methyl acrylate, n-propyl, double Lauryl Alcohol esters, silane coupler KH-560, peroxidating Benzoyl, water-repellent modified auxiliary agent and wear-resisting modified filler are auxiliary agent, and by the cooperation of base-material and auxiliary agent, obtained 3D for building is beaten Print material has excellent waterproof and anti-wear performance.Wherein, water-repellent modified auxiliary agent is prepared by following technique：By bentonite, Blanc fixe, nitrocotton, zinc oxide, mica powder, zeolite powder and the concentrated sulfuric acid are well mixed, and are heated up, and insulation, are then stirred, and are filtered, Washing is filtered, dried, grinding, sieving obtains material a to neutrality；Then by material a, carbamate, isopropyl acrylate, White carbon, tetraethyl orthosilicate and wood fibre are well mixed, and ultrasound-mechanical agitation is distributed to material b, Ran Houxiang in a water bath Silane coupling reagent KH-570 is added in material b and polyvinylpyrrolidone is well mixed, is heated up, and insulation, is led to during insulation Nitrogen, finally reaction product is poured out, add distilled water, stir, stratification, removed supernatant liquor, lower floor is reacted Product is filtered, and washing, is dried under vacuum to constant weight, is ground, and sieving, that is, obtains water-repellent modified auxiliary agent, applies to the present invention's In 3D printing material for building, coordinate with base-material, improve the combination degree with base-material, effectively increase 3D printing material of the present invention The water resistance of material.Wherein, wear-resisting modified filler is prepared by following technique：Phenolic resin and deionized water are mixed, so After heat up, be incubated, adjust pH, be subsequently added into 4- hydroxyphenyl-maleimides and be well mixed, heat up, insulation, adjust pH, then Add silica fibre and melamine is well mixed, cool, insulation, continue to cool down, discharge, be cooled to room temperature and obtain material A；By silicon Alkane coupling agent KH-550 and distilled water are well mixed, and are then placed in water-bath and are heated, and are subsequently added into material A, tapioca starch, kaolinite Soil, calcium carbonate, nanometer silicon carbide, Nano diamond and attapulgite are well mixed, ultrasonic disperse, then adjust pH, Ran Houfang Enter in water-bath and heat, then carry out separation of solid and liquid, by the distillation water washing of the solid after separation, then add n-butanol and steamed Dehydration is evaporated, then the powder after dehydration is put into baking oven and dried, room temperature is cooled to and obtains wear-resisting modified filler, apply to the present invention 3D printing material in, coordinate with major ingredient, effectively increase the anti-wear performance of 3D printing material of the present invention.The present invention's is for building 3D printing material has excellent waterproof and anti-wear performance.

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 be 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 Part, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 Part, 102 parts, 103 parts, 104 parts, 105 parts, 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；The parts by weight of Lauxite can be 30 parts, 35 parts, 40 Part, 45 parts, 50 parts；Polyacrylic parts by weight can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 Part, 34 parts, 35 parts；The parts by weight of makrolon can be 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 Part, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts；The parts by weight of end carboxyl nitrile rubber can Think 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts；The parts by weight of phenolic resin can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of trimethyl phosphate can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 Part, 7.5 parts, 8 parts；The parts by weight of glass fibre can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The parts by weight of carbon fiber can be with For 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The parts by weight of nylon can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 Part, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts；The parts by weight of multi-walled carbon nanotube can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts； The parts by weight of nano imvite can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts；The parts by weight of carbon black can be 2 parts, 2.5 parts, 3 Part, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of superfine silicon dioxide can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 Part, 4 parts；The parts by weight of polytetrafluoroethylene (PTFE) can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；The parts by weight of ALS can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of methyl acrylate can be 2 parts, 3 parts, 4 parts, 5 parts, 6 Part, 7 parts, 8 parts；The parts by weight of n-propyl 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 double Lauryl Alcohol esters can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 Part, 7 parts, 7.5 parts, 8 parts；Silane coupler KH-560 parts by weight can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；Benzoyl peroxide first The parts by weight of acyl 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, 6.5 parts, 7 Part, 7.5 parts, 8 parts；The parts by weight of water-repellent modified auxiliary agent can be 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 wear-resisting modified filler can be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts.

Embodiment 1

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 100 parts, 40 parts of Lauxite, 30 parts of polypropylene, 27 parts of makrolon, 45 parts of end carboxyl nitrile rubber, 3.5 parts of phenolic resin, 6 parts of trimethyl phosphate, 5 parts of glass fibre, 5 parts of carbon fiber, 6.5 parts of nylon, 4 parts of multi-walled carbon nanotube, 2 parts of nano imvite, 3.5 parts of carbon black, 2.5 parts of superfine silicon dioxide, 4 parts of polytetrafluoroethylene (PTFE), 3.5 parts of ALS, 5 parts of methyl acrylate, third 3.5 parts of olefin(e) acid n-propyl, 5.5 parts of double Lauryl Alcohol esters, 4 parts of silane coupler KH-560,4.5 parts of benzoyl peroxide, waterproof 10 parts of modified additive, 9 parts of wear-resisting modified filler.

Water-repellent modified auxiliary agent is prepared by following technique：By weight by 10 parts of bentonites, 4.5 parts of blanc fixes, 3.5 Part nitrocotton, 2.5 parts of zinc oxide, 4 parts of mica powders, 3.5 parts of zeolite powders and 5 parts of concentrated sulfuric acids are well mixed, and are warming up to 85 DEG C, insulation 10min, 3h then is stirred in 2000r/min rotating speeds, filtering, washs to neutrality, filters, dry, grinding, 200 mesh sieves is crossed and obtains Material a；Then by material a, 3.5 parts of carbamates, 3 parts of isopropyl acrylates, 4.5 parts of white carbons, 3.5 parts of positive silicic acid tetrems Ester and 2.5 parts of wood fibres are well mixed, and the scattered 3h of ultrasound-mechanical agitation obtains material b in 50 DEG C of water-baths, then to material 4.5 parts of Silane coupling reagent KH-570s are added in b and 6 parts of polyvinylpyrrolidones are well mixed, are warming up to 80 DEG C, are incubated 6h, are protected Lead to nitrogen in the process of temperature, finally pour out reaction product, add distilled water, stir, stratification, it is clear to remove upper strata Liquid, lower reaction product layer is filtered, washed, 800 DEG C are dried under vacuum to constant weight, grinding, cross 200 mesh sieves, that is, obtain waterproof Modified additive.

Wear-resisting modified filler is prepared by following technique：6 parts of phenolic resin and deionized water are mixed by weight, so After be warming up to 92.5 DEG C, be incubated 15min, adjust pH to 2.5, it is equal to be subsequently added into 4.5 parts of 4- hydroxyphenyl-maleimides mixing It is even, 97.5 DEG C are warming up to, is incubated 70min, adjusts pH to 7.5, is subsequently added into 3.5 parts of silica fibres and 4.5 parts of melamine mixing Uniformly, 82.5 DEG C are cooled to, is incubated 50min, 55 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By 5 parts of silane Coupling agent KH-550 and distilled water are well mixed, and are then placed in water-bath and are heated 30min, are subsequently added into material A, 4.5 portions of cassavas Powder, 3.5 parts of kaolin, 3 parts of calcium carbonate, 4.5 parts of nanometer silicon carbides, 3 parts of Nano diamonds and 6 parts of attapulgites are well mixed, Ultrasonic disperse 15min, pH to 3 is then adjusted, is then placed in water-bath and heats 30min, separation of solid and liquid is then carried out, after separation Solid distillation water washing 3 times, then add n-butanol and carry out distillation dehydration, the powder after dehydration is then put into 110 DEG C 2h is dried in baking oven, room temperature is cooled to and obtains wear-resisting modified filler.

Embodiment 2

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 80 Part, 50 parts of Lauxite, polipropene 25 part, 36 parts of makrolon, 30 parts of end carboxyl nitrile rubber, 5 parts of phenolic resin, tricresyl phosphate 4 parts of methyl esters, 6 parts of glass fibre, 2 parts of carbon fiber, nylon 9 part, 3 parts of multi-walled carbon nanotube, 3 parts of nano imvite, 2 parts of carbon black, 4 parts of superfine silicon dioxide, 2 parts of polytetrafluoroethylene (PTFE), 5 parts of ALS, 2 parts of methyl acrylate, 6 parts of n-propyl, Double 3 parts of Lauryl Alcohol esters, 6 parts of silane coupler KH-560,1 part of benzoyl peroxide, 15 parts of water-repellent modified auxiliary agent, wear-resisting change 6 parts of filler of property.

Water-repellent modified auxiliary agent is prepared by following technique：By weight by 5 parts of bentonites, 6 parts of blanc fixes, 2 parts of nitre Change cotton, 4 parts of zinc oxide, 3 parts of mica powders, 5 parts of zeolite powders and 1 part of concentrated sulfuric acid to be well mixed, be warming up to 90 DEG C, be incubated 5min, so 2h is stirred after 2500r/min rotating speeds, filtering, washs to neutrality, filters, dry, grinding, cross 250 mesh sieves and obtain material a；So Afterwards by material a, 2 parts of carbamates, 5 parts of isopropyl acrylates, 3 parts of white carbons, 5 parts of tetraethyl orthosilicates and 1 part of wooden fibre Dimension is well mixed, and the scattered 2h of ultrasound-mechanical agitation obtains material b in 55 DEG C of water-baths, and 6 parts of silane are then added into material b Coupling agent kh-570 and 4 parts of polyvinylpyrrolidones are well mixed, and are warming up to 85 DEG C, are incubated 5h, and nitrogen is led to during insulation, Finally reaction product is poured out, distilled water is added, stirs, stratification, supernatant liquor is removed, lower reaction product layer is entered Row filters, and washing, 850 DEG C are dried under vacuum to constant weight, grinding, crosses 150 mesh sieves, that is, obtains water-repellent modified auxiliary agent.

Wear-resisting modified filler is prepared by following technique：4 parts of phenolic resin and deionized water are mixed by weight, so After be warming up to 95 DEG C, be incubated 10min, adjust pH to 3, be subsequently added into 3 parts of 4- hydroxyphenyl-maleimides and be well mixed, heat up To 100 DEG C, 60min is incubated, pH to 8 is adjusted, is subsequently added into 2 parts of silica fibres and 8 parts of melamines are well mixed, be cooled to 80 DEG C, 60min is incubated, 50 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By 6 parts of silane resin acceptor kh-550s and Distilled water is well mixed, and is then placed in water-bath and is heated 25min, be subsequently added into material A, 6 parts of tapioca starch, 2 parts of kaolin, 5 parts Calcium carbonate, 3 parts of nanometer silicon carbides, 5 parts of Nano diamonds and 4 parts of attapulgites are well mixed, and ultrasonic disperse 20min, are then adjusted PH to 2.5 is saved, is then placed in water-bath and heats 35min, then carry out separation of solid and liquid, by the distillation water washing of the solid after separation 2 times, then add n-butanol and carry out distillation dehydration, then the powder after dehydration is put into 120 DEG C of baking ovens and dries 1h, is cooled to Room temperature obtains wear-resisting modified filler.

Embodiment 3

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 120 parts, 30 parts of Lauxite, 35 parts of polypropylene, 18 parts of makrolon, 60 parts of end carboxyl nitrile rubber, 2 parts of phenolic resin, phosphorus Sour 8 parts of trimethyl, 4 parts of glass fibre, 8 parts of carbon fiber, 4 parts of nylon, 5 parts of multi-walled carbon nanotube, 1 part of nano imvite, carbon black 5 Part, 1 part of superfine silicon dioxide, 6 parts of polytetrafluoroethylene (PTFE), 2 parts of ALS, 8 parts of methyl acrylate, n-propyl 1 It is part, 8 parts of double Lauryl Alcohol esters, 2 parts of silane coupler KH-560,8 parts of benzoyl peroxide, 5 parts of water-repellent modified auxiliary agent, wear-resisting 12 parts of modified filler.

Water-repellent modified auxiliary agent is prepared by following technique：By weight by 15 parts of bentonites, 3 parts of blanc fixes, 5 parts of nitre Change cotton, 1 part of zinc oxide, 5 parts of mica powders, 2 parts of zeolite powders and 9 parts of concentrated sulfuric acids to be well mixed, be warming up to 80 DEG C, be incubated 15min, so 4h is stirred after 1500r/min rotating speeds, filtering, washs to neutrality, filters, dry, grinding, cross 150 mesh sieves and obtain material a；So Afterwards by material a, 5 parts of carbamates, 1 part of isopropyl acrylate, 6 parts of white carbons, 2 parts of tetraethyl orthosilicates and 4 parts of wooden fibres Dimension is well mixed, and the scattered 4h of ultrasound-mechanical agitation obtains material b in 45 DEG C of water-baths, and 3 parts of silane are then added into material b Coupling agent kh-570 and 8 parts of polyvinylpyrrolidones are well mixed, and are warming up to 75 DEG C, are incubated 7h, and nitrogen is led to during insulation, Finally reaction product is poured out, distilled water is added, stirs, stratification, supernatant liquor is removed, lower reaction product layer is entered Row filters, and washing, 750 DEG C are dried under vacuum to constant weight, grinding, crosses 250 mesh sieves, that is, obtains water-repellent modified auxiliary agent.

Wear-resisting modified filler is prepared by following technique：8 parts of phenolic resin and deionized water are mixed by weight, so After be warming up to 90 DEG C, be incubated 20min, adjust pH to 2, be subsequently added into 6 parts of 4- hydroxyphenyl-maleimides and be well mixed, heat up To 95 DEG C, 80min is incubated, pH to 7 is adjusted, is subsequently added into 5 parts of silica fibres and 1 part of melamine is well mixed, be cooled to 85 DEG C, 40min is incubated, 60 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By 4 parts of silane resin acceptor kh-550s and distillation Water is well mixed, and is then placed in water-bath and is heated 35min, is subsequently added into material A, 3 parts of tapioca starch, 5 parts of kaolin, 1 part of carbonic acid Calcium, 6 parts of nanometer silicon carbides, 1 part of Nano diamond and 8 parts of attapulgites are well mixed, and ultrasonic disperse 10min, then adjust pH To 3.5, it is then placed in water-bath and heats 25min, then carry out separation of solid and liquid, by the distillation water washing 4 times of the solid after separation, Then add n-butanol and carry out distillation dehydration, then the powder after dehydration is put into 100 DEG C of baking ovens and dries 3h, is cooled to room temperature Obtain wear-resisting modified filler.

Embodiment 4

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 85 Part, 45 parts of Lauxite, 28 parts of polypropylene, 32 parts of makrolon, 35 parts of end carboxyl nitrile rubber, 4 parts of phenolic resin, tricresyl phosphate 5 parts of methyl esters, 5.5 parts of glass fibre, 3 parts of carbon fiber, nylon 8 part, 3.5 parts of multi-walled carbon nanotube, 2.5 parts of nano imvite, charcoal Black 3 parts, 3 parts of superfine silicon dioxide, 3 parts of polytetrafluoroethylene (PTFE), 4 parts of ALS, 3 parts of methyl acrylate, acrylic acid positive third 5 parts of ester, 4 parts of double Lauryl Alcohol esters, 5 parts of silane coupler KH-560,2 parts of benzoyl peroxide, 12 parts of water-repellent modified auxiliary agent, Wear-resisting 7 parts of modified filler.

Water-repellent modified auxiliary agent is prepared by following technique：By weight by 8 parts of bentonites, 5 parts of blanc fixes, 3 parts of nitre Change cotton, 3 parts of zinc oxide, 3.5 parts of mica powders, 4 parts of zeolite powders and 2 parts of concentrated sulfuric acids to be well mixed, be warming up to 88 DEG C, be incubated 8min, Then 2.5h is stirred in 2200r/min rotating speeds, filtering, washs to neutrality, filter, dry, grinding, crossed 245 mesh sieves and obtain material a；Then by material a, 3 parts of carbamates, 4 parts of isopropyl acrylates, 4 parts of white carbons, 4 parts of tetraethyl orthosilicates and 2 parts of wood Matter fiber is well mixed, and the scattered 2.5h of ultrasound-mechanical agitation obtains material b in 52 DEG C of water-baths, then adds 5 into material b Part Silane coupling reagent KH-570 and 5 parts of polyvinylpyrrolidones are well mixed, and are warming up to 82 DEG C, are incubated 5.5h, the process of insulation In lead to nitrogen, finally reaction product is poured out, add distilled water, stir, stratification, remove supernatant liquor, by lower floor Reaction product is filtered, and washing, 820 DEG C are dried under vacuum to constant weight, grinding, is crossed 180 mesh sieves, that is, is obtained water-repellent modified auxiliary agent.

Wear-resisting modified filler is prepared by following technique：5 parts of phenolic resin and deionized water are mixed by weight, so After be warming up to 94 DEG C, be incubated 12min, adjust pH to 2.8, be subsequently added into 4 parts of 4- hydroxyphenyl-maleimides and be well mixed, rise Temperature is incubated 65min to 99 DEG C, adjusts pH to 7.8, is subsequently added into 3 parts of silica fibres and 7 parts of melamines are well mixed, be cooled to 81 DEG C, 55min is incubated, 52 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By 5.5 parts of silane coupler KH- 550 and distilled water be well mixed, be then placed in water-bath and heat 28min, be subsequently added into material A, 5 parts of tapioca starch, 3 parts of kaolinites Soil, 4 parts of calcium carbonate, 4 parts of nanometer silicon carbides, 4 parts of Nano diamonds and 5 parts of attapulgites are well mixed, ultrasonic disperse 18min, Then pH to 2.8 is adjusted, is then placed in water-bath and heats 32min, then carry out separation of solid and liquid, the solid after separation is distilled Water washing 2 times, then add n-butanol and carry out distillation dehydration, then the powder after dehydration is put into 115 DEG C of baking ovens and dried 1.5h, it is cooled to room temperature and obtains wear-resisting modified filler.

Embodiment 5

The wear-resisting 3D printing material of a kind of building water-proof proposed by the present invention, its raw material include by weight：ABS resin 115 parts, 35 parts of Lauxite, 32 parts of polypropylene, 19 parts of makrolon, 55 parts of end carboxyl nitrile rubber, 3 parts of phenolic resin, phosphorus Sour 7 parts of trimethyl, 4.5 parts of glass fibre, 7 parts of carbon fiber, 5 parts of nylon, 4.5 parts of multi-walled carbon nanotube, nano imvite 1.5 Part, 4 parts of carbon black, 2 parts of superfine silicon dioxide, 5 parts of polytetrafluoroethylene (PTFE), 3 parts of ALS, 7 parts of methyl acrylate, acrylic acid 2 parts of n-propyl, 7 parts of double Lauryl Alcohol esters, 3 parts of silane coupler KH-560,7 parts of benzoyl peroxide, water-repellent modified auxiliary agent 8 Part, 11 parts of wear-resisting modified filler.

Water-repellent modified auxiliary agent is prepared by following technique：By weight by 12 parts of bentonites, 4 parts of blanc fixes, 4 parts of nitre Change cotton, 2 parts of zinc oxide, 4.5 parts of mica powders, 3 parts of zeolite powders and 8 parts of concentrated sulfuric acids to be well mixed, be warming up to 82 DEG C, be incubated 12min, Then 3.5h is stirred in 1800r/min rotating speeds, filtering, washs to neutrality, filter, dry, grinding, crossed 155 mesh sieves and obtain material a；Then by material a, 4 parts of carbamates, 2 parts of isopropyl acrylates, 5 parts of white carbons, 3 parts of tetraethyl orthosilicates and 3 parts of wood Matter fiber is well mixed, and the scattered 3.5h of ultrasound-mechanical agitation obtains material b in 48 DEG C of water-baths, then adds 4 into material b Part Silane coupling reagent KH-570 and 7 parts of polyvinylpyrrolidones are well mixed, and are warming up to 78 DEG C, are incubated 6.5h, the process of insulation In lead to nitrogen, finally reaction product is poured out, add distilled water, stir, stratification, remove supernatant liquor, by lower floor Reaction product is filtered, and washing, 780 DEG C are dried under vacuum to constant weight, grinding, is crossed 220 mesh sieves, that is, is obtained water-repellent modified auxiliary agent.

Wear-resisting modified filler is prepared by following technique：7 parts of phenolic resin and deionized water are mixed by weight, so After be warming up to 91 DEG C, be incubated 18min, adjust pH to 2.2, be subsequently added into 5 parts of 4- hydroxyphenyl-maleimides and be well mixed, rise Temperature is incubated 75min to 96 DEG C, adjusts pH to 7.2, is subsequently added into 4 parts of silica fibres and 2 parts of melamines are well mixed, be cooled to 84 DEG C, 45min is incubated, 58 DEG C is continued cool to, discharging, is cooled to room temperature and obtains material A；By 4.5 parts of silane coupler KH- 550 and distilled water be well mixed, be then placed in water-bath and heat 32min, be subsequently added into material A, 4 parts of tapioca starch, 4 parts of kaolinites Soil, 2 parts of calcium carbonate, 5 parts of nanometer silicon carbides, 2 parts of Nano diamonds and 7 parts of attapulgites are well mixed, ultrasonic disperse 12min, Then pH to 3.2 is adjusted, is then placed in water-bath and heats 28min, then carry out separation of solid and liquid, the solid after separation is distilled Water washing 4 times, then add n-butanol and carry out distillation dehydration, then the powder after dehydration is put into 105 DEG C of baking ovens and dried 2.5h, it is cooled to room temperature and obtains wear-resisting modified filler.

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

1. a kind of wear-resisting 3D printing material of building water-proof, it is characterised in that its raw material includes by weight：ABS resin 80- 120 parts, Lauxite 30-50 parts, -35 parts of polipropene 25, makrolon 18-36 parts, end carboxyl nitrile rubber 30-60 parts, phenol Urea formaldehyde 2-5 parts, trimethyl phosphate 4-8 parts, glass fibre 4-6 parts, carbon fiber 2-8 parts, nylon 4-9 parts, multi-walled carbon nanotube 3-5 parts, nano imvite 1-3 parts, carbon black 2-5 parts, superfine silicon dioxide 1-4 parts, polytetrafluoroethylene (PTFE) 2-6 parts, allyl sulphonic acid Sodium 2-5 parts, methyl acrylate 2-8 parts, n-propyl 1-6 parts, double Lauryl Alcohol ester 3-8 parts, silane coupler KH-560 2-6 parts, benzoyl peroxide 1-8 parts, water-repellent modified auxiliary agent 5-15 parts, wear-resisting modified filler 6-12 parts.

2. the wear-resisting 3D printing material of building water-proof according to claim 1, it is characterised in that the original of water-repellent modified auxiliary agent Material includes by weight：Bentonite 5-15 parts, blanc fixe 3-6 parts, nitrocotton 2-5 parts, zinc oxide 1-4 parts, mica powder 3-5 Part, zeolite powder 2-5 parts, concentrated sulfuric acid 1-9 parts, carbamate 2-5 parts, isopropyl acrylate 1-5 parts, white carbon 3-6 parts, positive silicon Sour tetra-ethyl ester 2-5 parts, wood fibre 1-4 parts, Silane coupling reagent KH-570 3-6 parts, polyvinylpyrrolidone 4-8 parts.

3. the wear-resisting 3D printing material of building water-proof according to claim 1 or 2, it is characterised in that water-repellent modified auxiliary agent Prepared by following technique：Bentonite, blanc fixe, nitrocotton, zinc oxide, mica powder, zeolite powder and the concentrated sulfuric acid are mixed Uniformly, heat up, insulation, then stir, filter, wash to neutrality, filter, dry, grinding, sieving obtains material a；Then by thing Material a, carbamate, isopropyl acrylate, white carbon, tetraethyl orthosilicate and wood fibre are well mixed, and are surpassed in a water bath Sound-mechanical agitation is distributed to material b, and Silane coupling reagent KH-570 and polyvinylpyrrolidone mixing are then added into material b Uniformly, heat up, insulation, nitrogen is led to during insulation, finally pours out reaction product, add distilled water, stir, stand Layering, supernatant liquor is removed, lower reaction product layer is filtered, washed, be dried under vacuum to constant weight, ground, sieving, that is, obtained Water-repellent modified auxiliary agent.

4. the wear-resisting 3D printing material of building water-proof according to claim any one of 1-3, it is characterised in that water-repellent modified Auxiliary agent is prepared by following technique：By bentonite, blanc fixe, nitrocotton, zinc oxide, mica powder, zeolite powder and the concentrated sulfuric acid It is well mixed, 80-90 DEG C is warming up to, is incubated 5-15min, then stirs 2-4h in 1500-2500r/min rotating speeds, is filtered, washing To neutrality, filter, dry, grinding, cross 150-250 mesh sieves and obtain material a；Then it is material a, carbamate, acrylic acid is different Propyl ester, white carbon, tetraethyl orthosilicate and wood fibre are well mixed, and ultrasound-mechanical agitation disperses 2- in 45-55 DEG C of water-bath 4h obtains material b, then adds Silane coupling reagent KH-570 into material b and polyvinylpyrrolidone is well mixed, be warming up to 75-85 DEG C, 5-7h is incubated, nitrogen is led to during insulation, finally pours out reaction product, distilled water is added, stirs, it is quiet Layering is put, supernatant liquor is removed, lower reaction product layer is filtered, is washed, 750-850 DEG C is dried under vacuum to constant weight, grinding, 150-250 mesh sieves are crossed, that is, obtain water-repellent modified auxiliary agent.

5. the wear-resisting 3D printing material of building water-proof according to claim any one of 1-4, it is characterised in that wear-resisting modification The original of filler includes by weight：Phenolic resin 4-8 parts, 4- hydroxyphenyl-maleimides 3-6 parts, silica fibre 2-5 parts, three Poly cyanamid 1-8 parts, silane resin acceptor kh-550 4-6 parts, tapioca starch 3-6 parts, kaolin 2-5 parts, calcium carbonate 1-5 parts, nano-sized carbon SiClx 3-6 parts, Nano diamond 1-5 parts, attapulgite 4-8 parts.

6. the wear-resisting 3D printing material of building water-proof according to claim any one of 1-5, it is characterised in that wear-resisting modification Filler is prepared by following technique：Phenolic resin and deionized water are mixed, then heated up, is incubated, pH is adjusted, is subsequently added into 4- hydroxyphenyl-maleimides are well mixed, and are heated up, and insulation, adjust pH, are subsequently added into silica fibre and melamine mixing is equal It is even, cool, insulation, continue to cool down, discharge, be cooled to room temperature and obtain material A；Silane resin acceptor kh-550 and distilled water are mixed Uniformly, it is then placed in water-bath and heats, is subsequently added into material A, tapioca starch, kaolin, calcium carbonate, nanometer silicon carbide, nanogold Hard rock and attapulgite are well mixed, and ultrasonic disperse, then adjust pH, are then placed in water-bath and are heated, and then carry out solid-liquid point From by the distillation water washing of the solid after separation, then addition n-butanol progress distillation dehydration, then puts the powder after dehydration Enter in baking oven and dry, be cooled to room temperature and obtain wear-resisting modified filler.

7. the wear-resisting 3D printing material of building water-proof according to claim any one of 1-6, it is characterised in that wear-resisting modification Filler is prepared by following technique：Phenolic resin and deionized water are mixed, then heat to 90-95 DEG C, is incubated 10- 20min, pH to 2-3 is adjusted, 4- hydroxyphenyl-maleimides is subsequently added into and is well mixed, be warming up to 95-100 DEG C, be incubated 60- 80min, pH to 7-8 is adjusted, silica fibre is subsequently added into and melamine is well mixed, be cooled to 80-85 DEG C, be incubated 40- 60min, 50-60 DEG C is continued cool to, discharging, room temperature is cooled to and obtains material A；Silane resin acceptor kh-550 and distilled water are mixed Close uniformly, be then placed in water-bath and heat 25-35min, be subsequently added into material A, tapioca starch, kaolin, calcium carbonate, nano silicon carbide Silicon, Nano diamond and attapulgite are well mixed, ultrasonic disperse 10-20min, are then adjusted pH to 2.5-3.5, are then placed in 25-35min is heated in water-bath, then carries out separation of solid and liquid, by the solid after separation with water washing is distilled 2-4 times, is then added N-butanol carries out distillation dehydration, and then the powder after dehydration is put into 100-120 DEG C of baking oven and dries 1-3h, room temperature is cooled to and obtains Wear-resisting modified filler.