CN105524401B - A kind of preparation method of ABS compositions for 3D printing - Google Patents
A kind of preparation method of ABS compositions for 3D printing Download PDFInfo
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- CN105524401B CN105524401B CN201610061151.7A CN201610061151A CN105524401B CN 105524401 B CN105524401 B CN 105524401B CN 201610061151 A CN201610061151 A CN 201610061151A CN 105524401 B CN105524401 B CN 105524401B
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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 kind of preparation method of the ABS compositions for 3D printing, in composition, ABS numerical value is 45~55 mass fractions；SEBS grafts are 8~14 mass fractions；PC PPO block copolymers are 23~34.4 mass fractions；Amino silicane coupling agent is 0.3~0.7 mass fraction；Nano filling is 5~9 mass fractions；Glass fibre is 5~12 mass fractions；0.6~1.1 part of antioxidant；Light stabilizer is 0.3~0.7 mass fraction；Above-mentioned composition is squeezed out into blending and increasing reaction by stretching to flow；Obtain the ABS compositions of 3D printing.The composition of the present invention has excellent melt-processed stability, tensile strength, rigidity and impact strength, applied to 3D printing medical assistance instrument, not only it can ensure the customization precision of printed product, but also can guarantee the intensity of product, it is ensured that safe handling of the sufferer in rehabilitation course.
Description
Technical field
The present invention relates to high molecular material and its processing and forming field, more particularly to a kind of ABS for 3D printing is combined
The preparation method of object.
Background technology
Industrialized civilization has greatly pushed the progress of human society, the people that unique child-care center of family of this mankind of the earth can nourish
Mouth quantity is also drastically expanded to 7,000,000,000 critical point within half a century.But change and the mankind of industrialized production, supply model
Living-pattern preservation also brings many negative effects, wherein needing the quantity of limbs/bone the disabled of medical rescue bright
Aobvious increase is exactly most prominent social concern.Traffic and sudden hurt accident, local war etc. also form to a certain extent
Huge limbs disability group.According to statistics, every year because of the death toll of unexpected injury, burn is only second to traffic accident, comes the
Two, and also there are a large amount of wounded to merge burn in traffic accident injury.China's burn annual morbidity is about 1.5%~2%,
I.e. there are about 20,000,000 people every year to be burnt in various degree.Wherein clinically seventy percent the wounded can use orthoses that rehabilitation is assisted to control
It treats, and orthoses needs replacing suitable species according to the rehabilitation of different phase.Burn rehabilitation with orthoses demand at least
At 15,000,000 sets or more, market potential annual more than 3,000,000,000.
In recent years, China's cerebral apoplexy causes the incidence of brain paralysis to be in " blowout " situation.China's prevalence rate of stroke in 2012
Reach 1.82%, the patients with cerebral apoplexy in estimation China 40 years old or more has 10,830,000 people, and patients with cerebral apoplexy is in eight or nine cases out of ten all adjoint
Drop foot, in addition children with cerebral palsy and paralysis of common peroneal nerve, brain trauma, below L4 cauda equina injury patients, have a net increase of every year
It is long to disable case close to 2,000,000.Wherein a large portion needs to implement foot correction rehabilitation, to the ankle of fixed personalized high rigidity
Orthopedic remedy instrument for foot demand is also growing.For patient lying in bed, most of spasm period patients are developed by abirritation period, are rectified
Shape device plays the role of pre- ankle-joint support and Varus deformity, so prevention is very important in advance.The annual market demand is 500
Ten thousand sets, market scale is at 50~6,000,000,000 yuan.
Since rehabilitation course is very long, can patient oneself is in adhere to that good reconditioning is a query, if when long
Between poor gait, eventually result in the lopsided development in joint.It is this kind of farthest to avoid the occurrence of, it needs to use
Personalized orthoses.For having generated the patient of orthodontic condition, using personalized orthoses, the rehabilitation of patient can be promoted to correct
Deformity.
Traditional industrialization manufacture framework is in the large-scale batch production of unified standard, although greatly embodying scale
Change, intensive production efficiency, but can not meet the needs of personalized.The appearance of 3D printing technique is intelligent, personalized
Manufacture provides reliable means, and personalized medical demand, is 3D printing technique in medical instrument especially auxiliary treatment
Or the application in rehabilitation field provides the tempting market space and the motive force of development.
Metal class product and high molecular material production can be divided by being presently used for the 3D printing product of medical assistance instrument field
Product.Metal class product is generally using selective laser sintering/cladding (SLS) technology, and high score subclass product is then generally using melting
Deposition modeling method (FDM).In view of the limitation of 3D printing technique at present, the theme of macromolecule 3D printing material be still ABS and its
Modified product, print temperature are generally 230~270 DEG C.Because ABS can only range generic engineering plastics, this material and match
The intensity and performance for covering 3D printing technique products obtained therefrom are only slightly higher than general thermoplastic, are extremely difficult to nylon, poly- carbonic acid
The class of one kind engineering plastics such as ester.Its static mechanical property and dynamic mechanical can not all be competent at daily need and frequently take exercise
The demand of the sufferer of rehabilitation.
If preparing such as PC/ABS, PA/ABS alloy using general method of modifying, these materials can not be complete at 270 DEG C
Full-fusing, processing rheological property is poor, and stress raisers can not be eliminated, and does not simply fail to ensure the intensity of product, and its 3D
The precision of printed product can not also ensure.The advantage of personalized customization also just can not be embodied in this way, can be brought when serious to sufferer
The safety of various troubles or even entail dangers to sufferer.
Exploitation not only has excellent machinability, but also can ensure that and realize personalized customization purpose, and then prepare with high-strength
The new A BS composite materials of the auxiliary treatment rehabilitation material of degree are one of key links for realizing its 3D printing medical equipment.
Invention content
In order to overcome the disadvantages mentioned above of the prior art with insufficient, the purpose of the present invention is to provide a kind of for 3D printing
There is excellent tensile strength, rigidity, endurance and melt-processed to stablize for the preparation method of ABS compositions, obtained material
Property prepares the medical assistance apparatus structure component of all kinds of personalized customization particularly suitable for fused glass pellet method (FDM) 3D printing
Production.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of ABS compositions for 3D printing, includes the following steps：
(1) material is weighed by following mass fraction：
(2) ABS, SEBS graft, PC-PPO block copolymers, Nano filling, glass fibre, amino silane are coupled
Agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed, and mixing temperature is 20~30 DEG C, and rotating speed is 100~300
Rev/min, incorporation time is 1~3 minute；
(3) it will be added in through the material after step (2) premixing from feeder and stretch stream extruder, melting extrusion is granulated, spiral shell
Bar rotating speed is 100~200 revs/min, and main feeder rotating speed is 10~60 revs/min, and each section of temperature of extruder is 190~250
℃。
Above-mentioned ABS resin be acrylonitrile-butadiene-styrene terpolymer (ABS), weight average molecular weight 150,
000-200,000g/mol, acrylonitrile (AN) content are 15~35 (quality) %.
Above-mentioned SEBS grafts are SEBS grafted maleic anhydrides (MAH), and grafting rate is 0.5~2.0 (quality) %.
The length of PC segments is between 30~100 in above-mentioned PC-PPO block copolymers, and the length of PPO segments is 20~30
Between.
Above-mentioned amino silicane coupling agent for gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-
Aminoethyl)-gamma-aminopropyl-triethoxy-silane, one kind in N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane or its
Combination.It is preferred that γ-aminopropyl triethoxysilane (trade name KH550).
Above-mentioned Nano filling preferred size is the bata-tricalcium phosphate of 100~300nm.
Above-mentioned glass fibre can be alkali-free thermoplastic assembled roving (chopped).
Above-mentioned antioxidant is made of primary antioxidant and auxiliary antioxidant, and the mass ratio of the two is 2~5：4~6.Wherein,
Primary antioxidant for antioxidant 1098 (N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and antioxygen
The compound of agent 1076 (β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid), the mass ratio of the two are
1：1.Auxiliary antioxidant is irgasfos 168 (three [2.4- di-tert-butyl-phenyls] phosphite esters).
Above-mentioned light stabilizer is (poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- three of light stabilizer 944
Piperazine -2,4- [(2,2,6,6,-tetramethyl-4-piperidyl) imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls)
Imino group] }).
Compared with prior art, the present invention has the following advantages and beneficial effect：
The present invention squeezes out blending and increasing reaction by stretching to flow, and significantly reduces ABS resin and PC-PPO block copolymers
Interfacial tension, enhance the compatibility of glass fibre and macromolecule resin.Due to the fusing point of PC-PPO block copolymers and soft
Change point all significantly lower than its bulk resin, be adaptive to relatively low 3D printing technique；By adding nanometer β-tricresyl phosphate
Calcium improves the melt-processed stability of 3D printing silk.Stretching stream extruder does not have apparent shear action, can be more reliably
Ensure the integrality of glass fibre, tensile strength, rigidity and the impact strength of composite material are increased substantially.Cause
This, ABS compositions of the invention are used for 3D printing medical assistance instrument, can not only ensure the customization precision of printed product, but also
It can guarantee the intensity of product, it is ensured that safe handling of the sufferer in rehabilitation course.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
In embodiment, ABS selects the PA757K of Qi Mei companies；SEBS grafts select Ke Teng companies of the U.S.
FG901G, grafting rate are 1.0~1.7 (quality) %；PC-PPO block copolymers are China Blue Star Group Co., Ltd.
Trial-production, the wherein length of PC segments is between 50~80, and the length of PPO segments is between 20~30；Amino silicane coupling agent is purchased
From Nanjing through Tian Wei Chemical Co., Ltd.s gamma-aminopropyl-triethoxy-silane, trade name KH550；Nano filling is homemade grain
Spend the bata-tricalcium phosphate in 100~300nm；Glass fibre is closed for the alkali-free thermoplastic of Jushi Group Co., Ltd.'s production
Stock roving 988A (long fine chopped)；Antioxidant 1098, antioxidant 1076, auxiliary antioxidant 168, light stabilizer 944 are
Ciba produces.
Preparation method includes step：
(1) it premixes：By ABS, SEBS graft, PC-PPO block copolymers, Nano filling, glass fibre, amino silane
Coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed, and mixing temperature is 20~30 DEG C, rotating speed 100
~300 revs/min, incorporation time is 1~3 minute.
(2) extruding pelletization：The material of premixing from feeder is added in and stretches stream extruder, melting extrusion is granulated, screw rod
Rotating speed is 100~200 revs/min, and main feeder rotating speed is 10~60 revs/min.Each section of temperature of extruder is 190~250 DEG C.
By being molded at 190~230 DEG C for the ABS composition grains material of 3D printing after 60~80 DEG C of forced air dryings
The test bars of national Specification test tensile property, impact property and fatigue performance respectively.
The mechanical property of ABS compositions according to the present invention for 3D printing is tested using national standard.
Fatigue performance then carries out 300,000 times tired on the MARSIII torque rheometers of ThermoFisher companies using the pattern of rocking
Labor is tested, and experimental temperature is room temperature, and it is 300,000 times, set of frequency 10Hz to rock number, and strain is set as 0.1%.Investigate sample
Whether item occurs phenomena such as damaged and stress whitening.
Embodiment 1
Each raw material is weighed according to following proportioning：ABS mass fractions are 55 parts, and SEBS grafts mass fraction is 8 parts,
PC-PPO block copolymers mass fraction is 23 parts, and nano-β-tricalcium phosphate mass fraction is 5 parts, and glass fiber quality number is
12 parts, amino silicane coupling agent KH550 mass fractions are 0.7 part, and primary antioxidant mass fraction is 0.4 part, irgasfos 168 quality
Number is 0.6 part, and 944 mass fraction of light stabilizer is 0.3 part.By ABS, SEBS graft, PC-PPO block copolymers, nanometer
Bata-tricalcium phosphate, glass fibre, amino silicane coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed,
Mixing temperature is 25 DEG C, and rotating speed is 150 revs/min, and incorporation time is 3 minutes.The material of premixing from feeder is added in and is drawn
Stream extruder is stretched, melting extrusion is granulated, and screw speed is 120 revs/min, and main feeder rotating speed is 20 revs/min.Extruder is each
Duan Wendu is 190~250 DEG C.Tie rod crosses water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
Embodiment 2
Each raw material is weighed according to following proportioning：ABS mass fractions are 50 parts, and SEBS grafts mass fraction is 10 parts,
PC-PPO block copolymers mass fraction is 28 parts, and nano-β-tricalcium phosphate mass fraction is 7 parts, and glass fiber quality number is
10 parts, amino silicane coupling agent KH550 mass fractions are 0.5 part, and primary antioxidant mass fraction is 0.5 part, irgasfos 168 quality
Number is 0.5 part, and 944 mass fraction of light stabilizer is 0.5 part.By ABS, SEBS graft, PC-PPO block copolymers, nanometer
Bata-tricalcium phosphate, glass fibre, amino silicane coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed,
Mixing temperature is 20 DEG C, and rotating speed is 200 revs/min, and incorporation time is 2 minutes.The material of premixing from feeder is added in and is drawn
Stream extruder is stretched, melting extrusion is granulated, and screw speed is 150 revs/min, and main feeder rotating speed is 30 revs/min.Extruder is each
Duan Wendu is 190~250 DEG C.Tie rod crosses water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
Embodiment 3
Each raw material is weighed according to following proportioning：ABS mass fractions are 45 parts, and SEBS grafts mass fraction is 14 parts,
PC-PPO block copolymers mass fraction is 34.4 parts, and nano-β-tricalcium phosphate mass fraction is 9 parts, glass fiber quality number
It it is 5 parts, amino silicane coupling agent KH550 mass fractions are 0.3 part, and primary antioxidant mass fraction is 0.2 part, irgasfos 168 matter
It is 0.4 part to measure number, and 944 mass fraction of light stabilizer is 0.7 part.By ABS, SEBS graft, PC-PPO block copolymers, receive
Rice bata-tricalcium phosphate, glass fibre, amino silicane coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are premixed
It closes, mixing temperature is 30 DEG C, and rotating speed is 180 revs/min, and incorporation time is 2.5 minutes.The material of premixing is added from feeder
Enter to stretch stream extruder, melting extrusion is granulated, and screw speed is 160 revs/min, and main feeder rotating speed is 40 revs/min.It squeezes out
Each section of temperature of machine is 190~250 DEG C.Tie rod crosses water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
Comparative example 1
Each raw material is weighed according to following proportioning：ABS mass fractions are 88.2 parts, and glass fiber quality number is 10 parts,
Amino silicane coupling agent KH550 mass fractions are 0.5 part, and primary antioxidant mass fraction is 0.3 part, irgasfos 168 mass fraction
It it is 0.5 part, 944 mass fraction of light stabilizer is 0.5 part.ABS, glass fibre, amino silicane coupling agent, antioxidant and light is steady
Determine agent and sequentially add mixing machine to be pre-mixed, mixing temperature is 25 DEG C, and rotating speed is 150 revs/min, and incorporation time is 3 minutes.
The material of premixing from feeder is added in and stretches stream extruder, melting extrusion is granulated, and screw speed is 150 revs/min, main to feed
Material machine rotating speed is 30 revs/min.Each section of temperature of extruder is 190~250 DEG C.Tie rod crosses water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
Comparative example 2
Each raw material is weighed according to following proportioning：ABS mass fractions are 83.2 parts, and SEBS grafts mass fraction is 5 parts,
Glass fiber quality number is 10 parts, and amino silicane coupling agent KH550 mass fractions are 0.5 part, and primary antioxidant mass fraction is
0.3 part, irgasfos 168 mass fraction is 0.5 part, and 944 mass fraction of light stabilizer is 0.5 part.By ABS, glass fibre, amino
Silane coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed, and mixing temperature is 25 DEG C, rotating speed 150
Rev/min, incorporation time is 3 minutes.The material of premixing from feeder is added in and stretches stream extruder, melting extrusion is granulated,
Screw speed is 150 revs/min, and main feeder rotating speed is 30 revs/min.Each section of temperature of extruder is 190~250 DEG C.Tie rod
Cross water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
Comparative example 3
Each raw material is weighed according to following proportioning：ABS mass fractions are 58.2 parts, PC-PPO block copolymer mass fractions
It it is 30 parts, glass fiber quality number is 10 parts, and amino silicane coupling agent KH550 mass fractions are 0.5 part, primary antioxidant quality
Number is 0.3 part, and irgasfos 168 mass fraction is 0.5 part, and 944 mass fraction of light stabilizer is 0.5 part.By ABS, glass fibers
Dimension, amino silicane coupling agent, antioxidant and light stabilizer sequentially add mixing machine and are pre-mixed, and mixing temperature is 25 DEG C, is turned
Speed is 150 revs/min, and incorporation time is 3 minutes.The material of premixing from feeder is added in and stretches stream extruder, melting is squeezed
Go out to be granulated, screw speed is 150 revs/min, and main feeder rotating speed is 30 revs/min.Each section of temperature of extruder is 190~250
℃.Tie rod crosses water pelletizing.
Test is used for the performance of the ABS compositions of 3D printing, and test result is shown in Table 1.
ABS composition of the table 1 for 3D printing matches and performance
In the present invention, ABS resin can also be other acrylonitrile-butadiene-styrene terpolymers, weight average molecular weight
It is 150,000~200,000g/mol, acrylonitrile content are 15~35wt%；SEBS grafts can also be that other SEBS are grafted horse
Carry out acid anhydrides, wherein grafting rate is 0.5~2.0wt%；PC-PPO block copolymers can also be other PC-PPO block copolymers,
The length of middle PC segments is between 30~100, and the length of PPO segments is between 20~30；Amino silicane coupling agent can also be γ-
Aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane,
One or more of N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane.The present invention can be also realized using the above scheme.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of ABS compositions for 3D printing, which is characterized in that include the following steps：
(1) material is weighed by following mass fraction：
(2) by ABS, SEBS graft, PC-PPO block copolymers, Nano filling, glass fibre, amino silicane coupling agent, anti-
Oxygen agent and light stabilizer sequentially add mixing machine and are pre-mixed, and mixing temperature is 20~30 DEG C, and rotating speed is 100~300 revs/min
Clock, incorporation time are 1~3 minute；
(3) draft flowing deformation extruder will be added in from feeder through the material after step (2) premixing, melting extrusion is granulated, screw rod
Rotating speed is 100~200 revs/min, and main feeder rotating speed is 10~60 revs/min, and each section of temperature of extruder is 190~250 DEG C；
The Nano filling is the bata-tricalcium phosphate that granularity is 100~300nm.
2. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the ABS trees
Fat is acrylonitrile-butadiene-styrene terpolymer, weight average molecular weight 150,000~200,000g/mol；Acrylonitrile
Content is 15~35wt%.
3. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the SEBS
Graft is SEBS grafted maleic anhydrides, and grafting rate is 0.5~2.0wt%.
4. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the PC-
The number of repetitive unit in PPO block copolymers in PC segments is between 30~100 (a), the repetitive unit in PPO segments
Number between 20~30 (a).
5. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the amino
Silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-ammonia third
One or more of ethyl triethoxy silicane alkane, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane.
6. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the glass
Fiber is chopped alkali-free thermoplastic assembled roving.
7. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the antioxygen
Agent includes primary antioxidant and auxiliary antioxidant；The mass ratio of primary antioxidant and auxiliary antioxidant is 2~5：4~6；
Wherein, the primary antioxidant is (N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and β-
The compound of the positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, the mass ratio of the two is 1：1；The auxiliary
Antioxidant is three [2.4- di-tert-butyl-phenyls] phosphite esters.
8. the preparation method of the ABS compositions according to claim 1 for 3D printing, which is characterized in that the light is steady
Determine agent for it is poly- [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- [(2,2,6,6,-tetramethyl-piperidines
Base) imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls) imino group].
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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 |
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| 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 |
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| EP2161125A1 (en) * | 2008-08-20 | 2010-03-10 | Bayer MaterialScience AG | Plastic compound moulded part in three layer construction |
| CN103980672A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing aromatic polyester material and preparation method thereof |
| CN104031304A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院化学研究所 | Ultraviolet light crosslinked polymer material used for 3D printing, and preparation method and application thereof |
| CN104072935A (en) * | 2014-06-13 | 2014-10-01 | 福来宝电子(深圳)有限公司 | ABS (acrylonitrile butadiene styrene) material used for 3D (three dimensional) printing and manufacturing process thereof |
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