CN105524401A - Preparation method of ABS (acrylonitrile butadiene styrene) composition for 3D printing - Google Patents
Preparation method of ABS (acrylonitrile butadiene styrene) composition for 3D printing Download PDFInfo
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- CN105524401A CN105524401A CN201610061151.7A CN201610061151A CN105524401A CN 105524401 A CN105524401 A CN 105524401A CN 201610061151 A CN201610061151 A CN 201610061151A CN 105524401 A CN105524401 A CN 105524401A
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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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- 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
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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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- 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
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Abstract
The invention discloses a preparation method of ABS (acrylonitrile butadiene styrene) composition for 3D printing. The composition comprises, in parts by mass, 45-55 parts of ABS, 8-14 parts of an SEBS (styrene-ethylene-butylenes-styrene) graft, 23-34.4 parts of a PC-PPO (polycarbonate-polyphenylene oxide) segmented copolymer, 0.3-0.7 parts of an amino silane coupling agent, 5-9 parts of nano filler, 5-12 parts of glass fibers, 0.6-1.1 parts of an antioxidant and 0.3-0.7 parts of a light stabilizer. The ABS composition for 3D printing is prepared through extrusion and blending of elongational flows as well as reactive compatibilization. The composition has good melt processing stability, good tensile strength, good rigidity and good anti-impact strength, and can guarantee customization precision of printed products and product strength and guarantee that a patient uses 3D printed products safely in the recovery process when the composition is applied to 3D printing aiding medical instruments.
Description
Technical field
The present invention relates to macromolecular material and forming process field thereof, particularly a kind of preparation method of the ABS composition for 3D printing.
Background technology
Industrialized civilization has greatly promoted the progress of human society, and the size of population that unique the child-care center of these mankind of the earth can nourish also sharply is expanded to the critical point of 7,000,000,000 within half a century.But the change of suitability for industrialized production, supply model and the change of human life style also bring many negative effects, the quantity showed increased wherein needing the limbs/bone the disabled of medical rescue is exactly the most outstanding social concern.Traffic and sudden hurt accident, local war etc. also define huge limbs disability colony to a certain extent.According to statistics, every year because of the death toll of unexpected injury, burn is only second to traffic accident, comes second, and also has a large amount of wounded to merge burn in traffic accident injury.China's burn annual morbidity is about 1.5% ~ 2%, namely about has 2,000 ten thousand people to suffer to burn in various degree every year.Wherein seventy percent the wounded can use orthopedic instrument to assist rehabilitation clinically, and orthopedic instrument needs to change suitable species according to the rehabilitation of different steps.More than burn rehabilitation at least overlaps 1,500 ten thousand by orthopedic instrument demand, market potential annual more than 3,000,000,000.
In recent years, China's cerebral apoplexy causes the sickness rate of brain paralysis in " blowout " situation.Within 2012, China's prevalence rate of stroke reaches 1.82%, existing 1,083 ten thousand people of patients with cerebral apoplexy of estimation China more than 40 years old, patients with cerebral apoplexy is in eight or nine cases out of ten all along with drop foot, add children with cerebral palsy, and paralysis of common peroneal nerve, cerebral trauma, below L4 cauda equina injury patient, have a net increase of every year and long to disable case close to 2,000,000.Wherein a large portion needs to implement foot correction rehabilitation, also growing to the ankle-foot orthosis demand of determining the high rigidity of personalization.For patient lying in bed, most of spasm period patient is developed by abirritation period, and orthopedic instrument plays the effect of pre-ankle-joint support and Varus deformity, so prevention is very important in advance.The annual market requirement is at 5,000,000 covers, and market scale is at 50 ~ 6,000,000,000 yuan.
Because rehabilitation course is very long, can patient oneself be in and adhere to that good reconditioning is a query, if long poor gait, finally can cause the lopsided development in joint.For farthest avoiding the generation of this kind of situation, need to use personalized orthopedic instrument.For the patient producing orthodontic condition, use personalized orthopedic instrument, the rehabilitation correction deformity of patient can be promoted.
Traditional industrialization manufactures framework in the large-scale batch production of unified standard, although greatly embody mass-producing, intensive production efficiency, demand that cannot be satisfying personalized.The appearance of 3D printing technique, for intelligent, individual character manufacturing provide reliable means, and the medical requirement of personalization, for 3D printing technique provides the tempting market space and the motive force of development in the application in medicine equipment especially assisting therapy or rehabilitation field.
At present, the 3D printed product for medical assistance instrument field can be divided into metal species product and macromolecular material product.Metal species product generally adopts selective laser sintering/cladding (SLS) technology, and polymer series products then generally adopts fused glass pellet method (FDM).In view of the restriction of current 3D printing technique, the theme of polymer 3D printed material remains ABS and modified product thereof, and print temperature is generally 230 ~ 270 DEG C.Because ABS can only range generic engineering plastics, this material and supporting 3D print the intensity of technique products obtained therefrom and performance just a little more than general thermoplastics, are difficult to reach the class of class engineering plastics such as nylon, polycarbonate.Its static mechanical property and dynamic properties all cannot be competent at the demand of the sufferer of the frequent training rehabilitation of daily need.
If adopt general method of modifying to prepare such as PC/ABS, PA/ABS alloy, these materials cannot melting completely at 270 DEG C, and processing rheological property is poor, and stress raisers cannot be eliminated, not only cannot ensure the intensity of goods, and the precision of its 3D printed product also cannot ensure.So also just can not embody the advantage of personalized customization, various trouble can be brought to sufferer time serious, even the safety of entail dangers to sufferer.
Exploitation both had excellent machinability, can guarantee again to realize personalized customization object, and then the new A BS matrix material preparing the assisting therapy rehabilitation material with high strength realizes its 3D to print one of key link of medical device.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of preparation method of the ABS composition for 3D printing, the material obtained has excellent tensile strength, rigidity, antifatigue and melt-processed stability, is particularly suited for the production that fused glass pellet method (FDM) 3D prints the medical assistance apparatus structure parts of all kinds of personalized customization of preparation.
Object of the present invention is achieved through the following technical solutions:
For a preparation method for the ABS composition that 3D prints, comprise the following steps:
(1) material is weighed by following massfraction:
(2) ABS, SEBS grafts, PC-PPO segmented copolymer, Nano filling, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carry out pre-mixing, mixing temperature is 20 ~ 30 DEG C, rotating speed is 100 ~ 300 revs/min, and mixing time is 1 ~ 3 minute;
(3) material after step (2) pre-mixing is added from feeding machine the stream forcing machine that stretches, melt extrude granulation, screw speed is 100 ~ 200 revs/min, and main feeding machine rotating speed is 10 ~ 60 revs/min, and forcing machine each section of temperature is 190 ~ 250 DEG C.
Above-mentioned ABS resin is acrylonitrile-butadiene-styrene terpolymer (ABS), and its weight-average molecular weight is 150,000-200,000g/mol, and vinyl cyanide (AN) content is 15 ~ 35 (quality) %.
Above-mentioned SEBS grafts is SEBS grafted maleic anhydride (MAH), and percentage of grafting is 0.5 ~ 2.0 (quality) %.
In above-mentioned PC-PPO segmented copolymer, the length of PC segment is between 30 ~ 100, and the length of PPO segment is between 20 ~ 30.
Above-mentioned amino silicane coupling agent is one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane or its combination.Preferred γ-aminopropyl triethoxysilane (trade(brand)name KH550).
Above-mentioned Nano filling preferred size is the bata-tricalcium phosphate of 100 ~ 300nm.
Above-mentioned glass fibre can be alkali-free thermoplastics assembled roving (short cut).
Above-mentioned oxidation inhibitor is made up of primary antioxidant and auxiliary antioxidant, and the mass ratio of the two is 2 ~ 5:4 ~ 6.Wherein, primary antioxidant is oxidation inhibitor 1098 (N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and antioxidant 1076 (β-(3; 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid) compound, the mass ratio of the two is 1:1.Auxiliary antioxidant is irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphorous acid ester).
Above-mentioned photostabilizer is photostabilizer 944 (poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-[(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two support [(2,2,6,6-tetramethyl--4-piperidyl) imino-]).
Compared with prior art, the present invention has the following advantages and beneficial effect:
The present invention extrudes blended and increasing reaction by stretching stream, significantly reduces the interfacial tension of ABS resin and PC-PPO segmented copolymer, enhances the consistency of glass fibre and macromolecule resin.Because the fusing point of PC-PPO segmented copolymer and softening temperature are all starkly lower than its bulk resin, be more adapted to relatively low 3D and print technique; The melt-processed stability that 3D prints silk is improved by adding nano-β-tricalcium phosphate.The stream forcing machine that stretches does not have obvious shearing action, and more reliably can ensure the integrity of glass fibre, the tensile strength of matrix material, rigidity and resistance to impact shock obtain and increase substantially.Therefore, ABS composition of the present invention is used for 3D and prints medical assistance apparatus, both can ensure the customization precision of printed product, can ensure again the intensity of product, guarantee the safe handling of sufferer in rehabilitation course.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In an embodiment, ABS selects the PA757K of Qi Mei company; SEBS grafts selects the FG901G of Ke Teng company of the U.S., and percentage of grafting is 1.0 ~ 1.7 (quality) %; PC-PPO segmented copolymer is China Blue Star Group Co., Ltd.'s trial-production, and wherein the length of PC segment is between 50 ~ 80, and the length of PPO segment is between 20 ~ 30; Amino silicane coupling agent purchased from Nanjing through Tian Wei Chemical Co., Ltd. γ-aminopropyl triethoxysilane, trade(brand)name KH550; Nano filling is the bata-tricalcium phosphate of homemade granularity at 100 ~ 300nm; Glass fibre is the alkali-free thermoplastics assembled roving 988A (long fibre is short to be cut) that Jushi Group Co., Ltd. produces; Oxidation inhibitor 1098, antioxidant 1076, auxiliary antioxidant 168, photostabilizer 944 are vapour Bagong department and produce.
Preparation method comprises step:
(1) premix: ABS, SEBS grafts, PC-PPO segmented copolymer, Nano filling, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 20 ~ 30 DEG C, rotating speed is 100 ~ 300 revs/min, and mixing time is 1 ~ 3 minute.
(2) extruding pelletization: the material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 100 ~ 200 revs/min, and main feeding machine rotating speed is 10 ~ 60 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.
The ABS composition grain material being used for 3D printing after 60 ~ 80 DEG C of forced air dryings is injection molded at 190 ~ 230 DEG C the test bars of national Specification, tests tensile property, impact property and fatigue performance respectively.
The mechanical property of the ABS composition for 3D printing involved in the present invention all adopts national standard to test.Fatigue performance then adopts the pattern of rocking to carry out the fatigue experiment of 300,000 times on the MARSIII torque rheometer of ThermoFisher company, and experimental temperature is room temperature, and rocking number of times is 300,000 times, and set of frequency is 10Hz, and strain is set to 0.1%.Investigate batten and whether the phenomenons such as damaged and stress whitening occur.
Embodiment 1
Each raw material is taken: ABS mass fraction is 55 parts according to following proportioning, SEBS grafts mass fraction is 8 parts, PC-PPO segmented copolymer mass fraction is 23 parts, nano-β-tricalcium phosphate mass fraction is 5 parts, glass fiber quality number is 12 parts, and amino silicane coupling agent KH550 mass fraction is 0.7 part, and primary antioxidant mass fraction is 0.4 part, irgasfos 168 mass fraction is 0.6 part, and photostabilizer 944 mass fraction is 0.3 part.ABS, SEBS grafts, PC-PPO segmented copolymer, nano-β-tricalcium phosphate, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 25 DEG C, rotating speed is 150 revs/min, and mixing time is 3 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 120 revs/min, and main feeding machine rotating speed is 20 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
Embodiment 2
Each raw material is taken: ABS mass fraction is 50 parts according to following proportioning, SEBS grafts mass fraction is 10 parts, PC-PPO segmented copolymer mass fraction is 28 parts, nano-β-tricalcium phosphate mass fraction is 7 parts, glass fiber quality number is 10 parts, and amino silicane coupling agent KH550 mass fraction is 0.5 part, and primary antioxidant mass fraction is 0.5 part, irgasfos 168 mass fraction is 0.5 part, and photostabilizer 944 mass fraction is 0.5 part.ABS, SEBS grafts, PC-PPO segmented copolymer, nano-β-tricalcium phosphate, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 20 DEG C, rotating speed is 200 revs/min, and mixing time is 2 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 150 revs/min, and main feeding machine rotating speed is 30 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
Embodiment 3
Each raw material is taken: ABS mass fraction is 45 parts according to following proportioning, SEBS grafts mass fraction is 14 parts, PC-PPO segmented copolymer mass fraction is 34.4 parts, nano-β-tricalcium phosphate mass fraction is 9 parts, glass fiber quality number is 5 parts, and amino silicane coupling agent KH550 mass fraction is 0.3 part, and primary antioxidant mass fraction is 0.2 part, irgasfos 168 mass fraction is 0.4 part, and photostabilizer 944 mass fraction is 0.7 part.ABS, SEBS grafts, PC-PPO segmented copolymer, nano-β-tricalcium phosphate, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 30 DEG C, rotating speed is 180 revs/min, and mixing time is 2.5 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 160 revs/min, and main feeding machine rotating speed is 40 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
Comparative example 1
Each raw material is taken: ABS mass fraction is 88.2 parts according to following proportioning, glass fiber quality number is 10 parts, amino silicane coupling agent KH550 mass fraction is 0.5 part, primary antioxidant mass fraction is 0.3 part, irgasfos 168 mass fraction is 0.5 part, and photostabilizer 944 mass fraction is 0.5 part.ABS, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 25 DEG C, and rotating speed is 150 revs/min, and mixing time is 3 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 150 revs/min, and main feeding machine rotating speed is 30 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
Comparative example 2
Each raw material is taken: ABS mass fraction is 83.2 parts according to following proportioning, SEBS grafts mass fraction is 5 parts, glass fiber quality number is 10 parts, amino silicane coupling agent KH550 mass fraction is 0.5 part, primary antioxidant mass fraction is 0.3 part, irgasfos 168 mass fraction is 0.5 part, and photostabilizer 944 mass fraction is 0.5 part.ABS, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 25 DEG C, and rotating speed is 150 revs/min, and mixing time is 3 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 150 revs/min, and main feeding machine rotating speed is 30 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
Comparative example 3
Each raw material is taken: ABS mass fraction is 58.2 parts according to following proportioning, PC-PPO segmented copolymer mass fraction is 30 parts, glass fiber quality number is 10 parts, amino silicane coupling agent KH550 mass fraction is 0.5 part, primary antioxidant mass fraction is 0.3 part, irgasfos 168 mass fraction is 0.5 part, and photostabilizer 944 mass fraction is 0.5 part.ABS, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carries out pre-mixing, mixing temperature is 25 DEG C, and rotating speed is 150 revs/min, and mixing time is 3 minutes.The material of pre-mixing is added from feeding machine the stream forcing machine that stretches, and melt extrude granulation, screw speed is 150 revs/min, and main feeding machine rotating speed is 30 revs/min.Forcing machine each section of temperature is 190 ~ 250 DEG C.Water pelletizing crossed by tie rod.
Test is used for the performance of the ABS composition that 3D prints, and test result is in table 1.
The ABS composition proportioning that table 1 prints for 3D and performance
In the present invention, ABS resin also can be other acrylonitrile-butadiene-styrene terpolymers, and its weight-average molecular weight is 150,000 ~ 200,000g/mol, and acrylonitrile content is 15 ~ 35wt%; SEBS grafts also can be other SEBS grafted maleic anhydrides, and wherein percentage of grafting is 0.5 ~ 2.0wt%; PC-PPO segmented copolymer also can be other PC-PPO segmented copolymers, and wherein the length of PC segment is between 30 ~ 100, and the length of PPO segment is between 20 ~ 30; Amino silicane coupling agent also can be in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane more than one.Adopt such scheme also can realize the present invention.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1., for a preparation method for the ABS composition of 3D printing, it is characterized in that, comprise the following steps:
(1) material is weighed by following massfraction:
(2) ABS, SEBS grafts, PC-PPO segmented copolymer, Nano filling, glass fibre, amino silicane coupling agent, oxidation inhibitor and photostabilizer are added mixing machine successively and carry out pre-mixing, mixing temperature is 20 ~ 30 DEG C, rotating speed is 100 ~ 300 revs/min, and mixing time is 1 ~ 3 minute;
(3) material after step (2) pre-mixing is added from feeding machine the stream forcing machine that stretches, melt extrude granulation, screw speed is 100 ~ 200 revs/min, and main feeding machine rotating speed is 10 ~ 60 revs/min, and forcing machine each section of temperature is 190 ~ 250 DEG C.
2. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, described ABS resin is acrylonitrile-butadiene-styrene terpolymer, and its weight-average molecular weight is 150,000 ~ 200,000g/mol; Acrylonitrile content is 15 ~ 35wt%.
3. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, described SEBS grafts is SEBS grafted maleic anhydride, and percentage of grafting is 0.5 ~ 2.0wt%.
4. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, in described PC-PPO segmented copolymer, the length of PC segment is between 30 ~ 100, and the length of PPO segment is between 20 ~ 30.
5. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, described amino silicane coupling agent is more than one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane.
6. the preparation method of ABS composition printed for 3D according to claim 1, is characterized in that, the bata-tricalcium phosphate of described Nano filling to be granularity be 100 ~ 300nm.
7. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, described glass fibre is the short alkali-free thermoplastics assembled roving cut.
8. the preparation method of the ABS composition for 3D printing according to claim 1, it is characterized in that, described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant; The mass ratio of primary antioxidant and auxiliary antioxidant is 2 ~ 5:4 ~ 6;
Wherein, described primary antioxidant is (N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and β-(3,5-di-tert-butyl-hydroxy phenyl) compound of the positive octadecanol ester of propionic acid, both mass ratioes are 1:1; Described auxiliary antioxidant is three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
9. the preparation method of the ABS composition for 3D printing according to claim 1, is characterized in that, described photostabilizer is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two support [(2,2,6,6-tetramethyl--4-piperidyl) imino-].
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| CN106046748A (en) * | 2016-07-09 | 2016-10-26 | 深圳市华普新材料有限公司 | 3D printing material |
| RU2641134C1 (en) * | 2016-07-14 | 2018-01-16 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Electrically conductive metal-filled polymer compound for 3d-printing (versions) |
| CN106633713A (en) * | 2016-10-18 | 2017-05-10 | 贵州当科技有限公司 | In-situ micro-glass-fiber reinforced polymer based 3D printing consumables as well as preparation method and equipment thereof |
| CN106566269A (en) * | 2016-10-20 | 2017-04-19 | 蒙宇 | Glass fiber composite material with high thermal deformation temperature and used for 3D printing |
| CN107141585A (en) * | 2017-05-05 | 2017-09-08 | 广州华新科实业有限公司 | A kind of string, its preparation method and application |
| 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 |
| CN108587040A (en) * | 2017-12-31 | 2018-09-28 | 芜湖林电子科技有限公司 | A kind of 3D printing ABS composite material and preparation method thereof that good toughness is ageing-resistant |
| CN108640680A (en) * | 2018-04-11 | 2018-10-12 | 杭州科技职业技术学院 | Nano powder material for 3D printing and preparation method thereof |
| CN110527297A (en) * | 2019-07-26 | 2019-12-03 | 华南理工大学 | A kind of silicon rubber composite material and preparation method thereof for fusion sediment 3D printing |
| CN110527297B (en) * | 2019-07-26 | 2022-02-15 | 华南理工大学 | Silicone rubber composite material for fused deposition 3D printing and preparation method thereof |
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