CN104559034A - Modified ABS resin for 3D printing as well as preparation method of modified ABS resin - Google Patents
Modified ABS resin for 3D printing as well as preparation method of modified ABS resin Download PDFInfo
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- CN104559034A CN104559034A CN201510009833.9A CN201510009833A CN104559034A CN 104559034 A CN104559034 A CN 104559034A CN 201510009833 A CN201510009833 A CN 201510009833A CN 104559034 A CN104559034 A CN 104559034A
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Abstract
The invention provides modified ABS resin for 3D printing as well as a preparation method of the modified ABS resin. The modified ABS resin for 3D printing provided by the invention is prepared from the following components in percentage by weight: 40-85% of ABS resin, 1-10% of modified nanoparticles, 10-40% of SAN resin and 4-30% of fiber enhanced ABS resin aggregates. The modified ABS resin for 3D printing prepared by the invention has relatively good toughness and mechanical property and is suitable for most FDM moulded 3D printers in the market, so that edge warping in the printing process can be effectively reduced.
Description
Technical field
The present invention relates to synthesis of polymer material and preparing technical field, be specifically related to a kind of 3D printing modified propylene nitrile-butadiene-styrene (ABS) resin and preparation method thereof.
Background technology
3D printing technique, rely on information technology, precision optical machinery and Materials science etc. multidisciplinary, academic name is called rapid shaping technique (RP:Rapid Prototyping Manufacturing), also referred to as increasing material manufacturing technology (AM:Additive Manufacturing).Ultimate principle is Layered manufacturing, successively superposes.One by design or the mode ready-made 3D model such as scanning is cut into unlimited multiple section according to a certain coordinate axis, then printing and being stacked into together by original position in layer, form the stereoscopic model of an entity, be similar to the integration in higher mathematics.
ABS resin is that butadiene rubber particles is dispersed in " island " type structure in acrylonitrile styrene resin (AS) external phase, the rigidity of resin and the elasticity of rubber are combined, not only there is tough, hard, just balanced mutually excellent mechanical characteristic, and have that chemical proofing is good, good stability of the dimension, good, the easy application of surface luster and easy coloring advantage.Be widely used in automobile industry, electrical instrumentation industry and mechanical industry etc.Also be one of resin material that 3D printing technique is conventional.SAN resin is styrene-acrylonitrile copolymer, has high thermal resistance, outstanding glossiness and resistant to chemical media, also has excellent hardness, rigidity, dimensional stability and higher supporting capacity, has extensive use in commercial market.
Nanoparticle is through microscopic examination, and it is by the less atom of number or molecular atom group or molecular group, and its surface atom is long-range order and the unordered amorphous layer of short distance; There is complete crystallization and periodic arrangement atom in particle core, but its structure and bulk sample slightly different.Just because of this special construction type of nanoparticle, nanoparticle surface energy and Surface binding energy are increased sharply, makes there is many dangling bondss and the surface atom lacking adjacent atom, can combine with other atom and settle out.Therefore, nanoparticle can be applicable to polymer-filled modification, develops high-performance, has the matrix material of specific function.
Due to the limitation of current 3D printing technique, general ABS resin material is used for 3D and prints, and print temperature is 230 ~ 270 DEG C of scopes, and its product strength is about 80% of same resin injecting products intensity, limits the use of ABS resin in 3D printing technique.Because 3D printer head Heating temperature most of on market is up to 270 DEG C, want the intensity and the toughness that improve ABS resin 3D printed product, the conventional resin as melt blending modifications such as PC/ABS, PA/ABS, its modified ABS resin can not have good melting effect at 270 DEG C, can not ensure the precision of 3D printed product, intensity raising is also not obvious.The price of 3D printed material is higher in the market simultaneously, is unfavorable for the promotion and application of 3D printing technique.
In sum, the ABS resin that current people commonly use and polyblend print for 3D, particularly Deformation In The Fdm Process principle (FDM) 3D printer effect is unsatisfactory, therefore, prints exploitation modified ABS material have important theory significance and using value for 3D.
Summary of the invention
For solving the problem, the invention provides a kind of 3D printing modified ABS resin, by mechanical property and the toughness of adding fiber reinforcement ABS resin pellet, modified Nano particle improves ABS resin, reduce resin shrinkage rate, for 3D printed product provides better mechanical property, and reduce ABS resin 3D printing alice problem.Add melting index, raising Resin Flow that SAN resin can improve ABS resin, to be applicable to the 3D printer of most of Deformation In The Fdm Process principle (FDM) on the market, and provide better molding effect.
The invention provides a kind of 3D printing modified ABS resin, the mass percent of described modified ABS resin consists of: ABS resin: 40 ~ 85%; Modified Nano particle: 1 ~ 10%; SAN resin: 10 ~ 40%; Fiber reinforcement ABS resin pellet: 4 ~ 30%.
The present invention is by adding the modified Nano particle that particle diameter is 1 ~ 100nm, good flexible interface layer is formed by equally distributed nanoparticle and polymeric matrix, because rigidity nanoparticle produces stress concentration effect, fine fisssure can be produced hold when polymer materials is subject to impacting, absorb certain striking energy, reach toughness reinforcing object.Described modified Nano particle is nano SiC, Nano-meter CaCO3
3, nanometer ZrO
3in one or more through surface modification treatment gained.Wherein particular determination is not had to the surface modifying method of nanoparticle, as long as modified Nano particle dispersion is good, particle diameter 1 ~ 100nm.
The present invention, by adding fiber reinforcement ABS resin pellet, improves the mechanical property of polymkeric substance, and effectively reduces resin shrinkage rate, prevents the generation of printed product alice.Fortifying fibre in fiber reinforcement ABS resin pellet of the present invention is carbon fiber or glass fibre, and fibre content is 25% ~ 35%, and staple length is 3 ~ 10mm.
ABS resin of the present invention and SAN resin are conventional use, as long as meet product performance design requirements, stability is good, the present invention is not particularly limited.
The present invention also provides the preparation method of above-mentioned a kind of 3D printing modified ABS resin; as follows: in proportion described ABS resin, modified Nano particle, SAN resin, fiber reinforcement ABS resin pellet to be passed through high-speed mixer evenly compounding, vacuum-drying; be added to twin screw extruder again and carry out melt blending modification; extruding pelletization or wire drawing, rolling, can obtain 3D printing modified ABS resin of the present invention.
Evenly blended for ensureing each component of resin, stable performance, preferably can adopt and prepare 3D printing modified ABS resin of the present invention with the following method.By part ABS resin and modified Nano particle in mass ratio 1:1 carry out evenly compounding, vacuum-drying by high-speed mixer, then carry out melt blending, granulation through single screw extrusion machine or twin screw extruder, obtain nanometer particle-modified ABS resin master batch; SAN resin and fiber reinforcement ABS resin pellet are passed through high-speed mixer evenly compounding, vacuum-drying in proportion, then carries out melt blending, granulation through single screw extrusion machine or twin screw extruder, obtain SAN resin modified fiber reinforcement ABS resin master batch.Remaining ABS resin, nanometer particle-modified ABS masterbatch, SAN resin modified fiber reinforcement ABS resin master batch etc. are all compounding by high-speed mixer, vacuum-drying; carry out blended, granulation through twin screw extruder again or directly extrude, wire drawing, rolling, obtain 3D printing modified ABS resin of the present invention.
The 3D printing modified ABS resin that the present invention makes is applicable to the 3D printer of most of Deformation In The Fdm Process principle on the market, and 230 ~ 270 DEG C can have better printing effect.By nanometer particle-modified and fiber reinforcement, its mechanics and the more original ABS resin of toughness are increased, tensile strength increases by 10 ~ 20%; Notched Izod impact strength increases by 15 ~ 40%.Inorganic nano-particle is owing to having larger specific surface area, and Monodispersed, in polymeric matrix, has certain compatibilization, contributes to polymer blending modification.Use fiber reinforcement ABS resin pellet, add in right amount, not only can improve the mechanical property of modified ABS resin, also effectively can prevent the generation of alice in print procedure.SAN resin and ABS resin consistency well, can increase the external phase of resin matrix, and appropriate interpolation significantly can improve the mobility of resin, makes modified resin be more suitable for 3D printing shaping.3D printing modified ABS resin of the present invention has good rigidity and toughness, effectively can avoid the generation of alice in print procedure, ensures 3D printed product quality.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preferred preparation method of 3D printing modified ABS resin of the present invention.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Weigh ABS resin 55kg, modified Nano CaCO in proportion
3particle 5kg, SAN resin 20kg, fiber reinforcement ABS resin pellet 20kg; after high-speed mixer is evenly compounding, is added to twin screw extruder carries out melt blending modification; each heating zone temperature is 185 ~ 205 DEG C; extruding pelletization or wire drawing, rolling, obtain 3D printing modified ABS resin of the present invention.
Embodiment 2
In order to make described each component of 3D printing modified ABS resin evenly blended, system is more stable.Following preferably preparation method can be adopted to be prepared.Fig. 1 is the schematic flow sheet that 3D of the present invention prints by the preferred preparation method of inorganic modified ABS resin, as shown in Figure 1, will take out 5kg and modified Nano CaCO in 55kg ABS resin
3particle 5kg carries out evenly compounding through high-speed mixer, after 90 DEG C of vacuum-drying 2 ~ 4h, then add twin screw extruder, and each heating zone temperature is 185 ~ 205 DEG C, after extruding pelletization, obtain Nano-meter CaCO3
3modified ABS resin master batch; Get SAN resin 20kg, 20kg is evenly compounding by high-speed mixer for fiber reinforcement ABS resin pellet, after 90 DEG C of vacuum-drying 2h, add twin screw extruder again, each heating zone temperature is 185 ~ 205 DEG C, obtains SAN resin modified fiber reinforcement ABS resin master batch after extruding pelletization; By above-mentioned obtained nano modification ABS resin master batch, SAN resin modified fiber reinforcement ABS resin master batch and remaining 50kgABS resin after high-speed mixer evenly compounding, 90 DEG C of vacuum-drying 2h, add twin screw extruder, each heating zone temperature is 185 ~ 205 DEG C, through extruding, wire drawing, obtains 3D printing modified ABS resin after rolling.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (4)
1. a 3D printing modified ABS resin, the mass percent of described modified ABS resin consists of: ABS resin: 40 ~ 85%; Modified Nano particle: 1 ~ 10%; SAN resin: 10 ~ 40%; Fiber reinforcement ABS resin pellet: 4 ~ 30%.
2. modified Nano particle is nano SiC, Nano-meter CaCO3 according to claim 1
3, nanometer ZrO
3in one or more through surface modification treatment gained; The particle diameter of described modified Nano particle is 1 ~ 100nm.
3. the fortifying fibre of the pellet of fiber reinforcement ABS resin is according to claim 1 carbon fiber or glass fibre, and fibre content is 25% ~ 35%, and staple length is 3 ~ 10mm.
4. can be prepared as follows according to 3D printing modified ABS resin described in claim 1 ~ 3:
By part ABS resin and modified Nano particle in mass ratio 1:1 by high-speed mixer evenly compounding, vacuum-drying, then carry out melt blending, granulation through single screw extrusion machine or twin screw extruder, obtain nanometer particle-modified ABS resin master batch; SAN resin and fiber reinforcement ABS resin pellet are pressed than evenly compounding by high-speed mixer, vacuum-drying, then carry out melt blending, granulation through single screw extrusion machine or twin screw extruder, obtain SAN modified fibre reinforced ABS masterbatch resin; By remaining ABS resin, nanometer particle-modified ABS resin master batch, SAN resin modified fiber reinforcement ABS resin master batch etc.; evenly compounding by high-speed mixer; vacuum-drying; again through twin screw extruder carry out blended, granulation or directly extrude, wire drawing, rolling, obtain 3D printing modified ABS resin of the present invention.
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| CN201510009833.9A CN104559034A (en) | 2015-01-09 | 2015-01-09 | Modified ABS resin for 3D printing as well as preparation method of modified ABS resin |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845031A (en) * | 2015-05-26 | 2015-08-19 | 江苏浩宇电子科技有限公司 | Preparation method for three-dimensional printing material |
| CN104845032A (en) * | 2015-05-26 | 2015-08-19 | 江苏浩宇电子科技有限公司 | Preparation method of toughened 3D (three-dimensional) printing consumables |
| CN104877297A (en) * | 2015-05-26 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Preparation method for easy-to-color 3D printing supplies |
| CN104893283A (en) * | 2015-05-26 | 2015-09-09 | 江苏浩宇电子科技有限公司 | Preparation method for wear-resistant 3D printing material |
| CN104945832A (en) * | 2015-06-29 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for enhancing hydrophilicity of ABS (acrylonitrile-butadiene-styrene) |
| CN105017704A (en) * | 2015-06-29 | 2015-11-04 | 苏州荣昌复合材料有限公司 | Plastic toughening modification method |
| CN105482353A (en) * | 2015-12-22 | 2016-04-13 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Wear resistant resin material composition for printer and preparation method as well as application of wear resistant resin |
| CN105524398A (en) * | 2015-12-25 | 2016-04-27 | 成都新柯力化工科技有限公司 | ABS rapid prototyping material used for 3D printing, and preparation method thereof |
| CN106987088A (en) * | 2017-05-17 | 2017-07-28 | 郴州金通信息科技有限公司 | A kind of carbon dope fiber nanometer sheet 3D printing modified ABS material and preparation method thereof |
| CN106987087A (en) * | 2017-05-17 | 2017-07-28 | 郴州金通信息科技有限公司 | A kind of 3D printing modified ABS and PS materials for mixing graphene nanometer sheet and aluminum oxide nanoparticle and preparation method thereof |
| CN107011620A (en) * | 2017-05-17 | 2017-08-04 | 郴州金通信息科技有限公司 | One kind mixes graphene nanometer sheet 3D printing modified ABS material and preparation method thereof |
| CN107011619A (en) * | 2017-05-17 | 2017-08-04 | 郴州金通信息科技有限公司 | 3D printing modified ABS and PVC material of a kind of carbon dope fiber nanometer sheet and silver nano-grain and preparation method thereof |
| CN107033532A (en) * | 2017-05-17 | 2017-08-11 | 郴州金通信息科技有限公司 | A kind of 3D printing modified ABS and PP materials for mixing boron nitride nanosheet and aluminum nitride nanometer particle and preparation method thereof |
| CN107043517A (en) * | 2017-05-17 | 2017-08-15 | 郴州金通信息科技有限公司 | One kind mixes boron nitride nanosheet 3D printing modified ABS material and preparation method thereof |
| CN107163426A (en) * | 2017-06-05 | 2017-09-15 | 中山大学惠州研究院 | A kind of 3D printing low warpage ABS material and preparation method thereof |
| CN108070194A (en) * | 2016-11-15 | 2018-05-25 | 宜兴市乐华冶金辅助材料有限公司 | A kind of glass fiber reinforced plastics composite material |
| CN108219349A (en) * | 2016-12-14 | 2018-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing modified ABS resin and preparation method thereof |
| CN108264725A (en) * | 2018-02-07 | 2018-07-10 | 中国科学院重庆绿色智能技术研究院 | A kind of high compression ratio 3D high emulates the preparation method and product for model of bootstrapping |
| CN109438866A (en) * | 2018-10-16 | 2019-03-08 | 吉林化工学院 | 3D printing carbon fiber/ABS composite material and preparation method thereof |
| CN109929212A (en) * | 2017-12-15 | 2019-06-25 | 南京机器人研究院有限公司 | A kind of 3D printing plastic material |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
| CN115195106A (en) * | 2022-06-30 | 2022-10-18 | 上海酷鹰机器人科技有限公司 | Printing process for vertical stacking molding |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845031A (en) * | 2015-05-26 | 2015-08-19 | 江苏浩宇电子科技有限公司 | Preparation method for three-dimensional printing material |
| CN104845032A (en) * | 2015-05-26 | 2015-08-19 | 江苏浩宇电子科技有限公司 | Preparation method of toughened 3D (three-dimensional) printing consumables |
| CN104877297A (en) * | 2015-05-26 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Preparation method for easy-to-color 3D printing supplies |
| CN104893283A (en) * | 2015-05-26 | 2015-09-09 | 江苏浩宇电子科技有限公司 | Preparation method for wear-resistant 3D printing material |
| CN104945832A (en) * | 2015-06-29 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for enhancing hydrophilicity of ABS (acrylonitrile-butadiene-styrene) |
| CN105017704A (en) * | 2015-06-29 | 2015-11-04 | 苏州荣昌复合材料有限公司 | Plastic toughening modification method |
| CN105482353A (en) * | 2015-12-22 | 2016-04-13 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Wear resistant resin material composition for printer and preparation method as well as application of wear resistant resin |
| CN105524398A (en) * | 2015-12-25 | 2016-04-27 | 成都新柯力化工科技有限公司 | ABS rapid prototyping material used for 3D printing, and preparation method thereof |
| CN108070194A (en) * | 2016-11-15 | 2018-05-25 | 宜兴市乐华冶金辅助材料有限公司 | A kind of glass fiber reinforced plastics composite material |
| CN108219349A (en) * | 2016-12-14 | 2018-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing modified ABS resin and preparation method thereof |
| CN107033532A (en) * | 2017-05-17 | 2017-08-11 | 郴州金通信息科技有限公司 | A kind of 3D printing modified ABS and PP materials for mixing boron nitride nanosheet and aluminum nitride nanometer particle and preparation method thereof |
| CN107011620A (en) * | 2017-05-17 | 2017-08-04 | 郴州金通信息科技有限公司 | One kind mixes graphene nanometer sheet 3D printing modified ABS material and preparation method thereof |
| CN107043517A (en) * | 2017-05-17 | 2017-08-15 | 郴州金通信息科技有限公司 | One kind mixes boron nitride nanosheet 3D printing modified ABS material and preparation method thereof |
| CN106987087A (en) * | 2017-05-17 | 2017-07-28 | 郴州金通信息科技有限公司 | A kind of 3D printing modified ABS and PS materials for mixing graphene nanometer sheet and aluminum oxide nanoparticle and preparation method thereof |
| CN106987088A (en) * | 2017-05-17 | 2017-07-28 | 郴州金通信息科技有限公司 | A kind of carbon dope fiber nanometer sheet 3D printing modified ABS material and preparation method thereof |
| CN107011619A (en) * | 2017-05-17 | 2017-08-04 | 郴州金通信息科技有限公司 | 3D printing modified ABS and PVC material of a kind of carbon dope fiber nanometer sheet and silver nano-grain and preparation method thereof |
| CN107163426A (en) * | 2017-06-05 | 2017-09-15 | 中山大学惠州研究院 | A kind of 3D printing low warpage ABS material and preparation method thereof |
| CN109929212A (en) * | 2017-12-15 | 2019-06-25 | 南京机器人研究院有限公司 | A kind of 3D printing plastic material |
| CN108264725A (en) * | 2018-02-07 | 2018-07-10 | 中国科学院重庆绿色智能技术研究院 | A kind of high compression ratio 3D high emulates the preparation method and product for model of bootstrapping |
| CN109438866A (en) * | 2018-10-16 | 2019-03-08 | 吉林化工学院 | 3D printing carbon fiber/ABS composite material and preparation method thereof |
| CN109438866B (en) * | 2018-10-16 | 2021-04-09 | 吉林化工学院 | Carbon fiber/ABS composite material for 3D printing and preparation method thereof |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
| CN114437496B (en) * | 2022-03-09 | 2024-01-02 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
| CN115195106A (en) * | 2022-06-30 | 2022-10-18 | 上海酷鹰机器人科技有限公司 | Printing process for vertical stacking molding |
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Application publication date: 20150429 |