CN108250693A - A kind of 3D printing material - Google Patents
A kind of 3D printing material Download PDFInfo
- Publication number
- CN108250693A CN108250693A CN201611236723.7A CN201611236723A CN108250693A CN 108250693 A CN108250693 A CN 108250693A CN 201611236723 A CN201611236723 A CN 201611236723A CN 108250693 A CN108250693 A CN 108250693A
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- printing material
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- antioxidant
- screw extruder
- double screw
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
Abstract
The present invention relates to a kind of 3D printing material, the 3D printing material includes the following raw material component and parts by weight：20 ~ 35 parts of 30 ~ 50 parts of PLA, PBS, 0.5 ~ 5 part of toughener, 1 ~ 5 part of reinforcing agent, 0.5 ~ 5 part of nucleating agent, 0.1 ~ 0.5 part of antioxidant.3D printing material has preferable toughness and impact strength in the present invention, and heat distortion temperature is high, the processing and molding being suitable in 3D printing technique.
Description
Technical field
The present invention relates to a kind of composite materials, and in particular to a kind of for material of 3D printing and preparation method thereof.
Background technology
Polylactic acid (PLA) has nontoxic, and without pungent smell, melting temperature is relatively low, degradable pollution-free, cooling meat
The advantages that rate is small, transparent easy dyeing all meets requirement of the 3D printing technique to polymer material；But the crystallinity of polylactic acid compared with
Ester bond bond energy is small in small, strand, and the factor being easily broken off causes that the heat distortion temperature of polylactic acid is low, impact strength is low, toughness
The defects of bad, causes the products application printed by polylactic acid range to be very restricted, it is, therefore, necessary to pass through modification
Come the defects of overcoming application of the polylactic acid in 3D printing material.
Poly butylene succinate (PBS), also referred to as polybutylene succinate or poly- succinic acid fourth diester, fusing point 105
DEG C, crystallization temperature is a kind of hypocrystalline with complete biodegradable ability at 61 DEG C or so, relative crystallinity 40-60%
Property resin.Poly butylene succinate is mainly the following advantage compared with other biological degradable material：(1) excellent power
Performance is learned, mechanical property is close to polypropylene (PP) and acrylonitrile-butadiene-styrene copolymer (ABS) plastics；(2) it processes
Performance protrudes, and PBS is that processing performance is best in existing degradation plastic, can be added directly on existing plastic processing common apparatus
Work is molded, and is most to be hopeful to realize one of industrialized biodegradable polymer；(3) heat resistance is good, thermal deformation temperature
Degree is high, different from the heat labile feature of other biodegradable plastics.
Invention content
The defects of it is an object of the invention to overcome the prior art, providing one kind has preferable toughness and impact strength,
The 3D materials of relatively low print temperature, to overcome the defects of 3D printing toughness of material is poor in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of 3D printing material, the 3D printing material
Including the following raw material component and parts by weight：
Preferably, the number-average molecular weight of the PLA is 10~200,000.Preferably, the number-average molecular weight of the PLA for 10~
150000.
Preferably, the number-average molecular weight of the PBS is 2~100,000.
Preferably, the toughener be maleic anhydride, cumyl peroxide, the bis- (tert-butyl peroxies of 2,5- dimethyl -2,5-
Base) hexane, one or more of ethylene-methyl acrylate-glyceryl methacrylate terpolymer.More preferably
Ground, the model AX8900 of the toughener.
Preferably, the reinforcing agent is selected from one or both of nano silicon dioxide and nano-calcium carbonate.It is more excellent
Selection of land, when the reinforcing agent is the mixture of nano silicon dioxide and nano-calcium carbonate, nano silicon dioxide and nano-calcium carbonate
The mass ratio of calcium is 1：(2~4).Preferably, the particle diameter of the nano silicon dioxide and the nano-calcium carbonate for 5~
20nm。
Preferably, the nucleating agent is selected from kaolin, calcium carbonate, hydrotalcite, mica, talcum powder, calcium sulfate crystal whiskers, illiteracy
One or more of de- soil and silica.
Preferably, the antioxidant is composite antioxidant, and composite antioxidant is by primary antioxidant 300 and auxiliary antioxidant
168 compositions, and the mass ratio of primary antioxidant 300 and auxiliary antioxidant 168 is 1：(2~5).
The invention also discloses a kind of methods for preparing 3D printing material as described above, include the following steps：
1) it is PLA and PBS is dry in vacuum drying chamber respectively；
2) raw material components are mixed according to parts by weight；
3) it adds in double screw extruder and squeezes out after mixing, 160~205 DEG C of the temperature of double screw extruder.
Preferably, in step 1), dry temperature is 30~60 DEG C in vacuum drying chamber.
Preferably, each area's temperature of the double screw extruder is：One area：160~170 DEG C；2nd area：170~180 DEG C；
3rd area：180~190 DEG C；4th area：190~200 DEG C；Extrusion temperature：200~205 DEG C.
Preferably, the engine speed of the double screw extruder is 350~380rpm, 23~30rpm of feeding rotating speed.
Disclosed herein as well is purposes of the 3D printing material as described above in 3D printing field.
3D printing material has preferable toughness and impact strength in the present invention, and heat distortion temperature is high, is suitable for 3D printing
Processing and molding in technology.
Specific embodiment
With reference to specific embodiment, the present invention is further explained, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, the protection domain being not intended to be limiting of the invention.The test method of actual conditions is not specified in the following example,
Usually according to normal condition or the condition proposed by according to each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the normally understood meaning of those skilled in the art of the present technique.Except used in embodiment specific method, equipment,
Outside material, according to record of the those skilled in the art to the grasp of the prior art and the present invention, it can also use and this
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Embodiment 1
3D printing material includes the following raw material component and parts by weight employed in the present embodiment：
Wherein, it is 20,000 that polylactic acid PLA, which is the number-average molecular weight that number-average molecular weight is 100,000, PBS,.The type of the toughener
Number be AX8900.The reinforcing agent is nano silicon dioxide.Antioxidant is composite antioxidant, and composite antioxidant composition is main antioxygen
The weight composition ratio of agent 300 and auxiliary anti-oxidant 168 is 1:3.Nucleating agent is kaolin.
30 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：165℃；2nd area：175℃；
3rd area：185℃；4th area：195℃；Extrusion temperature：200℃.The engine speed of double screw extruder be 360rpm, feeding rotating speed
For 25rpm.
Embodiment 2
The raw material components of 3D printing material and the parts by weight of each component are as follows in the present embodiment：
The number-average molecular weight that wherein number-average molecular weight of polylactic acid (PLA) is 150,000, PBS is 20,000.Toughener is
AX8900.The reinforcing agent is selected from nano silicon dioxide.Antioxidant is composite antioxidant, is resisted based on composite antioxidant composition
The weight composition ratio of oxygen agent 300 and auxiliary anti-oxidant 168 is 1:2.
40 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：170℃；2nd area：180℃；
3rd area：190℃；4th area：200℃；Extrusion temperature：205℃.The engine speed of double screw extruder be 380rpm, feeding rotating speed
For 30rpm.
Embodiment 3
The raw material components and parts by weight of 3D printing material described in the present embodiment are as follows：
Wherein the number-average molecular weight of polylactic acid (PLA) is 120,000, and antioxidant is composite antioxidant, and composite antioxidant composition is
The weight composition ratio of primary antioxidant 300 and auxiliary anti-oxidant 168 is 1:4；The model AX8900 of the toughener；The PBS
Number-average molecular weight be 50,000.The reinforcing agent is nano-calcium carbonate.The nucleating agent is hydrotalcite.
50 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：170~175 DEG C；2nd area：
1175~80 DEG C；3rd area：180~185 DEG C；4th area：195~200 DEG C；Extrusion temperature：200~205 DEG C.Double screw extruder
Engine speed is 350rpm, and feeding rotating speed is 28rpm.
Embodiment 4
The raw material components and parts by weight of 3D printing material described in the present embodiment are as follows：
Wherein the number-average molecular weight of polylactic acid (PLA) is 140,000, and antioxidant is composite antioxidant, and composite antioxidant composition is
The weight composition ratio of primary antioxidant 300 and auxiliary anti-oxidant 168 is 1:5；The model AX8900 of the toughener；The PBS
Number-average molecular weight be 100,000.Mixture of the reinforcing agent for nano-calcium carbonate and nano silicon dioxide, nanometer titanium dioxide
The mass ratio of silicon and nano-calcium carbonate is 1：4.The nucleating agent is talcum powder.
60 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：170~175 DEG C；2nd area：
1175~80 DEG C；3rd area：180~185 DEG C；4th area：195~200 DEG C；Extrusion temperature：200~205 DEG C.Double screw extruder
Engine speed is 350rpm, and feeding rotating speed is 28rpm.
Embodiment 5
The raw material components and parts by weight of 3D printing material described in the present embodiment are as follows：
Wherein the number-average molecular weight of polylactic acid (PLA) is 200,000, and antioxidant is composite antioxidant, and composite antioxidant composition is
The weight composition ratio of primary antioxidant 300 and auxiliary anti-oxidant 168 is 1:3；The model AX8900 of the toughener；The PBS
Number-average molecular weight be 30,000.Mixture of the reinforcing agent for nano-calcium carbonate and nano silicon dioxide, nano silicon dioxide
Mass ratio with nano-calcium carbonate is 1：2.The nucleating agent is mica.
55 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：162~165 DEG C；2nd area：
172~175 DEG C；3rd area：182~185 DEG C；4th area：192~195 DEG C；Extrusion temperature：200~205 DEG C.Double screw extruder
Engine speed is 350rpm, and feeding rotating speed is 30rpm.
Embodiment 6
The raw material components and parts by weight of 3D printing material described in the present embodiment are as follows：
Wherein the number-average molecular weight of polylactic acid (PLA) is 100,000, and antioxidant is composite antioxidant, and composite antioxidant composition is
The weight composition ratio of primary antioxidant 300 and auxiliary anti-oxidant 168 is 1:2；The model AX8900 of the toughener；The PBS
Number-average molecular weight be 40,000.The reinforcing agent is nano-calcium carbonate and nano silicon dioxide, nano-calcium carbonate and nano-silica
The mass ratio of SiClx is 1:4.The nucleating agent is montmorillonite.
35 DEG C of dryings in vacuum drying chamber respectively by PLA and PBS；By PLA, PBS, toughener, reinforcing agent, nucleating agent and
Antioxidant is added in double screw extruder and is squeezed out, and each area's temperature of double screw extruder is：One area：160~165 DEG C；2nd area：
170~175 DEG C；3rd area：180~185 DEG C；4th area：190~195 DEG C；Extrusion temperature：200~205 DEG C.Double screw extruder
Engine speed is 375rpm, and feeding rotating speed is 27rpm.
3D printing material in Examples 1 to 6 is tested, and test result is as follows：
By data in above-mentioned table 1 it can be found that the 3D printing material being claimed in the embodiment of the present invention has preferably
Toughness and impact strength, heat distortion temperature is high, the processing and molding being suitable in 3D printing technique.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of the method for the present invention is not departed from, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made still fall within the range of technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of 3D printing material, which is characterized in that the 3D printing material includes the following raw material component and parts by weight：
2. 3D printing material as described in claim 1, which is characterized in that the number-average molecular weight of the PLA is 10~10,000.
3. 3D printing material as described in claim 1, which is characterized in that the number-average molecular weight of the PBS is 2~10 hundred million.
4. 3D printing material as described in claim 1, which is characterized in that the toughener be maleic anhydride, peroxidating diisopropyl
Benzene, bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-, ethylene-methyl acrylate-glyceryl methacrylate ternary
One or more of copolymer.
5. 3D printing material as described in claim 1, which is characterized in that the reinforcing agent is selected from nano silicon dioxide and receives
One or both of rice calcium carbonate.
6. 3D printing material as described in claim 1, which is characterized in that the nucleating agent is selected from kaolin, calcium carbonate, neatly
One or more of stone, mica, talcum powder, calcium sulfate crystal whiskers, montmorillonite and silica.
7. 3D printing material as described in claim 1, which is characterized in that the antioxidant be composite antioxidant, compound antioxygen
Agent is made of primary antioxidant 300 and auxiliary antioxidant 168, and the mass ratio of primary antioxidant 300 and auxiliary antioxidant 168 is 1：(2
~5).
8. a kind of preparation method of the 3D printing material as described in any one of claim 1~7, includes the following steps：
1) it is PLA and PBS is dry in vacuum drying chamber respectively；
2) raw material components are mixed according to parts by weight；
3) it adds in double screw extruder and squeezes out after mixing, 160~205 DEG C of the temperature of double screw extruder.
9. preparation method as claimed in claim 8, which is characterized in that each area's temperature of the double screw extruder is：One area：
160~170 DEG C；2nd area：170~180 DEG C；3rd area：180~190 DEG C；4th area：190~200 DEG C；Extrusion temperature：200~205
℃。
10. purposes of the 3D printing material in 3D printing field as described in any one of claim 1~7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611236723.7A CN108250693A (en) | 2016-12-28 | 2016-12-28 | A kind of 3D printing material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611236723.7A CN108250693A (en) | 2016-12-28 | 2016-12-28 | A kind of 3D printing material |
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| CN108250693A true CN108250693A (en) | 2018-07-06 |
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ID=62719601
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| CN201611236723.7A Pending CN108250693A (en) | 2016-12-28 | 2016-12-28 | A kind of 3D printing material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484707A (en) * | 2020-05-29 | 2020-08-04 | 浙江海正生物材料股份有限公司 | 3D printing polylactic resin material and preparation method thereof |
| CN112048162A (en) * | 2020-08-21 | 2020-12-08 | 江西格林美资源循环有限公司 | Full-biodegradable modified plastic for plastic-uptake thin-wall products and preparation method thereof |
| CN114249975A (en) * | 2021-12-30 | 2022-03-29 | 芜湖诺磊自动化科技有限公司 | High-ductility and easily-degradable 3D printing consumable and preparation method thereof |
| CN114685882A (en) * | 2022-04-03 | 2022-07-01 | 杭州师范大学 | Reactive micro-crosslinked elastomer and preparation method and application thereof |
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| US20120252977A1 (en) * | 2011-03-30 | 2012-10-04 | Xueyuan Zhu | Polylactic acid compositions, polylactic acid materials and methods of preparing the same |
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN105017734A (en) * | 2015-07-10 | 2015-11-04 | 清华大学 | Polymeric material for 3D printing and preparation method of polymeric material |
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2016
- 2016-12-28 CN CN201611236723.7A patent/CN108250693A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120252977A1 (en) * | 2011-03-30 | 2012-10-04 | Xueyuan Zhu | Polylactic acid compositions, polylactic acid materials and methods of preparing the same |
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN105017734A (en) * | 2015-07-10 | 2015-11-04 | 清华大学 | Polymeric material for 3D printing and preparation method of polymeric material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484707A (en) * | 2020-05-29 | 2020-08-04 | 浙江海正生物材料股份有限公司 | 3D printing polylactic resin material and preparation method thereof |
| CN112048162A (en) * | 2020-08-21 | 2020-12-08 | 江西格林美资源循环有限公司 | Full-biodegradable modified plastic for plastic-uptake thin-wall products and preparation method thereof |
| CN112048162B (en) * | 2020-08-21 | 2022-12-13 | 江西格林循环产业股份有限公司 | Full-biodegradable modified plastic for plastic-uptake thin-wall products and preparation method thereof |
| CN114249975A (en) * | 2021-12-30 | 2022-03-29 | 芜湖诺磊自动化科技有限公司 | High-ductility and easily-degradable 3D printing consumable and preparation method thereof |
| CN114685882A (en) * | 2022-04-03 | 2022-07-01 | 杭州师范大学 | Reactive micro-crosslinked elastomer and preparation method and application thereof |
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