CN108219349A - A kind of 3D printing modified ABS resin and preparation method thereof - Google Patents

A kind of 3D printing modified ABS resin and preparation method thereof Download PDF

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Publication number
CN108219349A
CN108219349A CN201611149042.7A CN201611149042A CN108219349A CN 108219349 A CN108219349 A CN 108219349A CN 201611149042 A CN201611149042 A CN 201611149042A CN 108219349 A CN108219349 A CN 108219349A
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China
Prior art keywords
abs resin
modified
printing
fiber reinforcement
resin
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Pending
Application number
CN201611149042.7A
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Chinese (zh)
Inventor
隋尊阳
刘刚
谢众
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Heilongjiang Xinda Enterprise Group Co Ltd
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Heilongjiang Xinda Enterprise Group Co Ltd
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Priority to CN201611149042.7A priority Critical patent/CN108219349A/en
Publication of CN108219349A publication Critical patent/CN108219349A/en
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

The present invention provides a kind of 3D printing modified ABS resin and preparation method thereof, and the mass percentage composition of 3D printing provided by the invention modified ABS resin is：ABS resin：40~85%；Modified Nano particle：1~10%；SAN resins：10~40%；Fiber reinforcement ABS resin pellet：4~30%.3D printing modified ABS resin prepared by the present invention, there is preferable toughness and mechanical property, is molded 3D printer suitable for the most of FDM in market, can effectively reduce the generation of alice in print procedure.

Description

A kind of 3D printing modified ABS resin and preparation method thereof
Technical field
The present invention relates to synthesis of polymer materials and preparing technical field, and in particular to a kind of 3D printing modified propylene Nitrile-butadiene-styrene（ABS）Resin and preparation method thereof.
Background technology
3D printing technique, it is multidisciplinary to rely on information technology, precision machinery and material science etc., academic entitled quick Forming technique（RP: Rapid Prototyping Manufacturing）, also referred to as increases material manufacturing technology（AM: Additive Manufacturing）.Basic principle is Layered manufacturing, is successively superimposed.It is ready-made by the modes such as designing or scanning one 3D models are cut into unlimited number of section according to a certain reference axis, then printing and being accumulated by original position in layer To together, the three-dimensional model of an entity is formed, similar to the integration in higher mathematics.
ABS resin is that butadiene rubber particles are dispersed in acrylonitrile-styrene resin continuous phase " island " type structure, The elasticity of the rigidity of resin and rubber is combined, the excellent mechanical characteristic not only with the equilibrium of tough, hard, firm phase, but also had Chemical resistance is good, good stability of the dimension, lustrous surface are good, easy application and the advantages of easy coloring.It is widely used in automobile making Industry, electrical instrumentation industry and mechanical industry etc..It is also one of common resin material of 3D printing technique.SAN resins for styrene- Acrylonitrile copolymer has heat-resisting quantity, outstanding glossiness and resistant to chemical media, also excellent hardness, rigidity, size Stability and higher bearing capacity, have extensive use in commercial market.
Nano-particle is atom group or molecular group by small numbers of atom or molecular composition through microexamination, Surface atom is long-range order and the unordered amorphous layer of short distance；In particle core, there are complete crystallizations and periodic arrangement Atom, but its structure and bulk sample are slightly different.Just because of this special construction type of nano-particle, make nanoparticle Sublist face can increase sharply with Surface binding energy, make to have many dangling bonds and lack the surface atom of adjacent atom, Ke Yiyu Other atoms are combined and settle out.Therefore, nano-particle can be applied to polymer-filled modification, and exploitation high-performance has The composite material of specific function.
Due to the limitation of current 3D printing technique, general ABS resin material is used for 3D printing, print temperature 230 ~ 270 DEG C of ranges, product strength are about the 80% of same resin injecting products intensity, limit ABS resin in 3D printing technique Use.Since most of 3D printer die heating temperature is up to 270 DEG C in the market, want to improve ABS resin 3D printing production The intensity and toughness of product commonly use the resin that such as PC/ABS, PA/ABS melt blending are modified, and modified ABS resin is at 270 DEG C There can not be melting effect well, it is impossible to ensure the precision of 3D printing product, intensity raising is not obvious.Existing market simultaneously The higher price of upper 3D printing material, is unfavorable for the promotion and application of 3D printing technique.
In conclusion the common ABS resin of people and plastic alloy are used for 3D printing, particularly Deformation In The Fdm Process at present Principle（FDM）3D printer effect is unsatisfactory, therefore, has important theoretical meaning for 3D printing exploitation modified ABS material Justice and application value
Invention content
To solve the above problems, the present invention provides a kind of 3D printing modified ABS resin, by adding fiber reinforcement ABS Resin granular material, modified Nano particle improve the mechanical property of ABS resin and toughness, reduce resin shrinkage rate, are produced for 3D printing Product provide better mechanical property, and reduce ABS resin 3D printing alice problem.Addition SAN resins can improve the molten of ABS resin Melt index, improve Resin Flow, to be suitable for most of Deformation In The Fdm Process principles on the market（FDM）3D printer, and Better molding effect is provided.
The present invention provides a kind of 3D printing modified ABS resin, and the mass percentage composition of the modified ABS resin is： ABS resin：40~85%；Modified Nano particle：1~10%；SAN resins：10~40%；Fiber reinforcement ABS resin pellet：4~30%.
The present invention is by adding the modified Nano particle that grain size is 1 ~ 100nm, by equally distributed nano-particle with gathering Close object matrix form good flexible interface layer, due to rigid nano-particle generate stress concentration effect, when polymer material by It is held to fine fisssure can be generated during impact, absorbs certain impact energy, reach toughening purpose.The modified Nano particle for nano SiC, Obtained by one or more surface-modified processing in nm level CaCO_3, nanometer ZrO3.Wherein to the surface modification side of nano-particle Method is there is no particular determination, as long as modified Nano particle good dispersion, 1 ~ 100nm of grain size.
The present invention improves the mechanical property of polymer, and effectively reduce resin by adding fiber reinforcement ABS resin pellet Shrinking percentage prevents the generation of printed product alice.Reinforcing fiber in fiber reinforcement ABS resin pellet of the present invention is fine for carbon Dimension or glass fibre, fiber content are 25% ~ 35%, and fibre length is 3 ~ 10mm.
ABS resin and SAN resin of the present invention is conventional use of, as long as meeting properties of product design requirement, performance Stability is good, and the present invention is not particularly limited.
It is as follows the present invention also provides a kind of above-mentioned preparation method of 3D printing modified ABS resin：In proportion by described in ABS resin, modified Nano particle, SAN resins, fiber reinforcement ABS resin pellet are uniformly compounded by high-speed mixer, vacuum is done It is dry, it adds to double screw extruder and carries out melt blending modification, extruding pelletization or wire drawing, winding, you can obtain institute of the present invention State 3D printing modified ABS resin.
To ensure that the blending of resin each component is uniform, performance is stablized, and preferably prepares 3D of the present invention with the following method Printing modified ABS resin.By part ABS resin and modified Nano particle in mass ratio 1:1 is carried out by high-speed mixer Even compounding, vacuum drying, then melt blending, granulation are carried out through single screw extrusion machine or double screw extruder, obtain nano-particle Modified ABS resin master batch；SAN resins and fiber reinforcement ABS resin pellet are uniformly compounded, very by high-speed mixer in proportion Sky is dry, then carries out melt blending through single screw extrusion machine or double screw extruder, is granulated, and obtains the increasing of SAN resin modifieds fiber Strong ABS resin master batch.By remaining ABS resin, nanometer particle-modified ABS masterbatch, SAN resin modified fiber reinforcement ABS resins Master batch etc. is compounded by high-speed mixer, is dried in vacuo, then be blended, be granulated or directly extruded through double screw extruder, Wire drawing, winding obtain 3D printing modified ABS resin of the present invention.
The modified ABS resin of 3D printing made of the present invention is suitable for the 3D of most of Deformation In The Fdm Process principle on the market Printer, 230 ~ 270 DEG C can have preferable printing effect.Make its mechanics and toughness more former by nanometer particle-modified and fiber reinforcement There is ABS resin to increase, tensile strength increases by 10 ~ 20%；Notch impact strength increases by 15 ~ 40%.Inorganic nano-particle due to With larger specific surface area, Monodispersed in a polymer matrix, has certain compatibilization, and polymer blending is contributed to change Property.It is appropriate to add using fiber reinforcement ABS resin pellet, the mechanical property of modified ABS resin can be not only improved, it can also It effectively prevent the generation of alice in print procedure.SAN resins and ABS resin compatibility are good, can increase the continuous of resin matrix Phase, appropriate addition can greatly improve the mobility of resin, and modified resin is made to be more suitable for 3D printing molding.3D printing of the present invention is used Modified ABS resin has preferable rigidity and toughness, and the generation of alice is can effectively avoid in print procedure, ensures 3D printing product Quality.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in the embodiment of the present invention Technical solution is clearly and completely described, it is clear that described embodiment is part of the embodiment of the present invention rather than complete The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts All other embodiments obtained shall fall within the protection scope of the present invention.
Embodiment 1
ABS resin 55kg, modificated nano-CaCO_3 particle 5kg, SAN resin 20kg, fiber reinforcement ABS resin grain are weighed in proportion Expect 20kg, added in after high-speed mixer is uniformly compounded to double screw extruder and carry out melt blending modification, each bringing-up section temperature It it is 185 ~ 205 DEG C, extruding pelletization or wire drawing, winding obtain 3D printing modified ABS resin of the present invention.
Embodiment 2
In order to make each component blending of the 3D printing modified ABS resin uniform, system is more stablized.It can be used following preferred It is prepared by preparation method.The flow of the 3D printing of the present invention preferred preparation method of inorganic modified ABS resin, by 55kg ABS trees 5kg and modificated nano-CaCO_3 particle 5kg is taken out in fat to be uniformly compounded through high-speed mixer, after 90 DEG C of 2 ~ 4h of vacuum drying, Double screw extruder is added, each bringing-up section temperature is 185 ~ 205 DEG C, and nm level CaCO_3 modified ABS tree is obtained after extruded granulation Fat master batch；SAN resins 20kg, fiber reinforcement ABS resin pellet 20kg is taken uniformly to be compounded by high-speed mixer, 90 DEG C of vacuum are done After dry 2h, double screw extruder is added, each bringing-up section temperature is 185 ~ 205 DEG C, and SAN resin modifieds are obtained after extruded granulation Fiber reinforcement ABS resin master batch；By nano modification ABS resin master batch obtained above, SAN resin modified fiber reinforcement ABS trees Fat master batch and remaining 50kgABS resins are uniformly compounded, through high-speed mixer after 90 DEG C of vacuum drying 2h, add in twin-screw Extruder, each bringing-up section temperature are 185 ~ 205 DEG C, and 3D printing modified ABS resin is obtained after extruded, wire drawing, winding.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although ginseng The present invention is described in detail according to foregoing embodiments, it will be understood by those of ordinary skill in the art that：It still may be used Either which part or all technical features are carried out etc. with modifying to the technical solution recorded in foregoing embodiments With replacement；And these modifications or replacement, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution Range.

Claims (4)

1. a kind of 3D printing modified ABS resin, the mass percentage composition of the modified ABS resin are：ABS resin：40~ 85%；Modified Nano particle：1~10%；SAN resins：10~40%；Fiber reinforcement ABS resin pellet：4~30%.
2. modified Nano particle is one or more in nano SiC, nm level CaCO_3, nanometer ZrO3 according to claim 1 Obtained by surface-modified processing；The grain size of the modified Nano particle is 1 ~ 100nm.
3. the reinforcing fiber of fiber reinforcement ABS resin pellet is carbon fiber or glass fibre according to claim 1, fiber contains It is 25% ~ 35% to measure, and fibre length is 3 ~ 10mm.
4. it can be prepared as follows according to claim 1 ~ 3 3D printing with modified ABS resin：By part ABS resin With modified Nano particle in mass ratio 1:1 is uniformly compounded by high-speed mixer, is dried in vacuo, then through single screw extrusion machine or double Screw extruder carries out melt blending, is granulated, and obtains nanometer particle-modified ABS resin master batch；By SAN resins and fiber reinforcement ABS resin pellet is pressed than by the uniform compounding of high-speed mixer, vacuum drying, then through single screw extrusion machine or double screw extruder It carries out melt blending, be granulated, obtain SAN modified fibre reinforced ABS masterbatch resins；By remaining ABS resin, nanometer particle-modified ABS resin master batch, SAN resin modified fiber reinforcement ABS resin master batches etc., are uniformly compounded by high-speed mixer, vacuum drying, Be blended, be granulated or directly extruded using double screw extruder, wire drawing, winding, obtain 3D printing of the present invention with changing Property ABS resin.
CN201611149042.7A 2016-12-14 2016-12-14 A kind of 3D printing modified ABS resin and preparation method thereof Pending CN108219349A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111040369A (en) * 2019-12-20 2020-04-21 佛山科学技术学院 High-strength plastic and preparation method and application thereof
CN113387606A (en) * 2021-07-01 2021-09-14 四川谦宜复合材料有限公司 Cement-based basalt fiber aggregate for 3D printing and preparation and use methods thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122121A (en) * 2013-03-11 2013-05-29 浙江誉隆科技发展有限公司 Nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof
CN104559034A (en) * 2015-01-09 2015-04-29 机械科学研究总院先进制造技术研究中心 Modified ABS resin for 3D printing as well as preparation method of modified ABS resin
CN105778484A (en) * 2016-03-15 2016-07-20 东华大学 Modified nylon material for 3D printing applied to FDM (fused deposition molding) technology and printing method of modified nylon material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122121A (en) * 2013-03-11 2013-05-29 浙江誉隆科技发展有限公司 Nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof
CN104559034A (en) * 2015-01-09 2015-04-29 机械科学研究总院先进制造技术研究中心 Modified ABS resin for 3D printing as well as preparation method of modified ABS resin
CN105778484A (en) * 2016-03-15 2016-07-20 东华大学 Modified nylon material for 3D printing applied to FDM (fused deposition molding) technology and printing method of modified nylon material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111040369A (en) * 2019-12-20 2020-04-21 佛山科学技术学院 High-strength plastic and preparation method and application thereof
CN113387606A (en) * 2021-07-01 2021-09-14 四川谦宜复合材料有限公司 Cement-based basalt fiber aggregate for 3D printing and preparation and use methods thereof

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