CN105504713B - A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere - Google Patents
A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere Download PDFInfo
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- CN105504713B CN105504713B CN201511002069.9A CN201511002069A CN105504713B CN 105504713 B CN105504713 B CN 105504713B CN 201511002069 A CN201511002069 A CN 201511002069A CN 105504713 B CN105504713 B CN 105504713B
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- polylactic acid
- acid microsphere
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
It is material modified with polylactic acid microsphere the invention provides a kind of 3D printing, it is characterised in that to be prepared from by weight by following components：100 parts of polylactic acid microsphere, 35 parts of graphene oxide, 1~10 part of heat stabilizer, 0.1~10 part of antioxidant, 0.1~10 part of defoamer, 0.1~10 part of levelling agent；The compound constituted by adding graphene oxide and heat stabilizer Ca Zn composite thing and ultra-fine hydrotalcite can significantly improve the powder flowbility and heat endurance of material, available for the accurate product of 3D printing, the heat endurance and toughness of product can be significantly improved, and simple production process, it is environment friendly and pollution-free, it can be directly used for 3D printing.
Description
Technical field
The present invention relates to technical field of macromolecules, and in particular to a kind of polylactic acid microsphere it is material modified and preparation method thereof with
Its application in 3D printing.
Background technology
3D printing technique is a kind of based on mathematical model file, and material can be bonded with powdery metal or plastics etc.
Material, come the technology of constructed object by way of successively printing.General principle is layered manufacturing, successively increases material to generate three
Tie up the technology of entity.At present, 3D printing technique is applied primarily to product prototype, Making mold and artistic creation, jewelry
The fields such as making, substitute the retrofit technique that these tradition are relied on.In addition, 3D printing technique is gradually applied to medical science, life
The fields such as thing engineering, building, clothes, aviation, wide space has been opened up for innovation.
Polymer microballoon material is as functional high molecule material, in analytical chemistry, biochemistry and other new and high technologies
Had a wide range of applications in field.Wherein PLA（PLA）Microballoon is due to fully biodegradable and with renewable money
Source is the plant origin of raw material, most potential biological degradation polyalcohol material is described as, so polylactic acid microsphere system
The research of standby technology is very active.Prepare the known method of polylactic acid microsphere have emulsification-solidification method, spray drying process and
Solvent-nonsolvent method.Wherein the most commonly used is emulsification-solidification method, and its implementation means is organic molten for PLA is dissolved in
In agent, under stirring by surfactant by its stable dispersion in aqueous, formed emulsion, with the volatilization of solvent, gather breast
Acid droplet gradually solidified forming.
China Patent Publication No. CN103146164A discloses a kind of poly- breast nano material toughened for rapid shaping
Sour material and preparation method thereof, this method is that polyacrylic acid ester microsphere and PLA are blended using double screw extruder
Extrusion is modified, although enhance the toughness of PLA, but the impact strength not to PLA is low and heat distortion temperature is low carries out
It is modified to improve, and carry out melt blending modification using double screw extruder, it is impossible to microballoon is formed, without powder flowbility.
Therefore the heat distortion temperature of polylactic acid microsphere is low, the defect that impact strength is low, toughness is bad, causes to be beaten by polylactic acid microsphere
Print off the products application scope come to be very restricted, it is, therefore, necessary to overcome polylactic acid microsphere in 3D printing by modified
The defect of application in material.
The present invention is to be modified polylactic acid microsphere, forms a kind of particle diameter micro- in 10-25um uniform-spherical PLA
Ball.The preparation method of the polylactic acid microsphere used is shown in China Patent Publication No. CN103172876 A, and it, which is used, uses higher boiling
Solvent is dissolved after PLA and derivant, carries out separation of solid and liquid with precipitating reagent, and obtains polylactic acid microsphere after drying, and what is obtained is
A kind of polyphosphazene polymer lactic acid microspheres material of size tunable, good dispersion.
The content of the invention
There is the poor defect of poor fluidity, heat endurance for 3D printing for current polylactic acid microsphere, the present invention is provided
A kind of polylactic acid microsphere is material modified, and the polylactic acid microsphere is material modified to have good powder flowbility and heat endurance,
The printing of 3D powder can be achieved.The material modified preparation method of the polylactic acid microsphere is further provided for, using homogenizer, successively
Adding polylactic acid microsphere, graphene oxide, heat stabilizer, toughener, antioxidant, defoamer, levelling agent mixes its high-speed stirred
Close uniform, the material modified good fluidity of prepared polylactic acid microsphere, with excellent heat endurance and toughness, production technology letter
It is single, it is environment friendly and pollution-free, it can be directly used for 3D printing.
To achieve the above object, the present invention uses following technical scheme：
A kind of 3D printing is material modified with polylactic acid microsphere, it is characterised in that be prepared from by weight by following components：
100 parts of polylactic acid microsphere
3-5 parts of graphene oxide
1~10 part of heat stabilizer
0.1~10 part of antioxidant
0.1~10 part of defoamer
0.1~10 part of levelling agent
Described polylactic acid microsphere molecular weight is more than 100,000 and particle diameter is 5um~15um.
Described heat stabilizer is the compound that Ca Zn composite thing and ultra-fine hydrotalcite are constituted, and its compound proportioning is calcium salt：
Zinc salt：Hydrotalcite=1：1：5, hydrotalcite is the white powder of layer structure, and its particle diameter is 10nm~100nm, and specific surface area is
10m2∕g~30m2∕g。
Described antioxidant is 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxy phenyls）Sulphur
At least one in ether, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters.
Described defoamer be dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone in extremely
Few one kind.
Described levelling agent is organosilicon-epoxide ethane copolymer, organosilicon-epoxide propane copolymer and poly dimethyl silicon
At least one in oxygen alkane.
The material modified preparation method of a kind of polylactic acid microsphere, it is characterised in that preparation method is as follows：
1）By weight, at room temperature so that under 1000-1400r/min speed conditions, into container, addition is poly- successively
100 parts of lactic acid microspheres, 3-5 parts of graphene oxide, 1~10 part of heat stabilizer, 0.1~10 part of antioxidant, defoamer 0.1~10
Part, 0.1~10 part of levelling agent, high-speed stirred 10min~30min are sufficiently mixed；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：
100~120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down and obtained by spray drying exit
High fluidity polylactic acid microsphere is material modified.
The present invention is more than 100,000 to molecular weight and particle diameter is modified for 5um~15um polylactic acid microsphere, adds oxidation
The compound of graphene and heat stabilizer Ca Zn composite thing and ultra-fine hydrotalcite composition can significantly improve the flow of powder of material
Property and heat endurance, available for the accurate product of 3D printing, the heat endurance and toughness of product can be significantly improved.
It is a further object to provide the material modified application in 3D printing of above-mentioned polylactic acid microsphere, beat 3D
Print technology is more widely used.
Beneficial effects of the present invention have：
1st, the present invention adds graphene oxide and heat stabilizer, antioxidant, defoamer and levelling agent in polylactic acid microsphere
It is modified, material flowability is good, while improving the heat endurance and toughness of material；
2nd, the material modified preparation technology of polylactic acid microsphere of the present invention is simple and environmentally-friendly pollution-free, low cost of manufacture；
3rd, the material modified uniform particle sizes of polylactic acid microsphere of the present invention, good fluidity is stable, can be directly through 3D printing equipment system
Standby is baroque accurate product, can significantly improve the heat endurance and toughness of printing product.Beaten according to ASTM D256 detections
The impact strength of part is printed, it is good using the toughness of products height of the material modified 3D printing of polylactic acid microsphere of the present invention, heat endurance.
Embodiment
Present invention is further described with reference to instantiation, but this should not be interpreted as to the model of the present invention
Enclose and be only limitted to following example, any simple change or equivalent based on made by the above-mentioned way of thinking of the invention all should belong to
Within scope of the present invention.Unless otherwise instructed, number is parts by weight described in each embodiment.
The specific embodiment of the present invention is as follows：
Embodiment 1
(1) raw material is equipped with the following proportions：
100 parts of polylactic acid microsphere,
1 part of heat stabilizer Ca Zn composite organic matter and ultra-fine hydrotalcite compound,
3 parts of graphene oxide,
Antioxidant 2,1 part of 6- three-level butyl -4- methylphenols,
Antioxidant is double（3,5- three-level butyl -4- hydroxy phenyls）1 part of thioether,
1 part of defoamer dimethyl polysiloxane,
1 part of defoamer ethylene oxide propylene oxide copolyether,
Levelling agent organosilicon-epoxide ethane copolymer 1 part,
1 part in levelling agent dimethyl silicone polymer.
1）By weight, at room temperature so that under 1000-1400r/min speed conditions, into container, addition is poly- successively
Lactic acid microspheres, graphene oxide, heat stabilizer, antioxidant, defoamer, levelling agent, high-speed stirred 10min~30min are fully mixed
Close；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：
100~120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down and obtained by spray drying exit
High fluidity polylactic acid microsphere is material modified.
The main performance of polylactic acid microsphere by pure polylactic acid microsphere with being modified is detected that testing result is as follows：
| Detection project | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Impact strength（J/m） | 15 | 36 |
| Heat distortion temperature（℃） | 60 | 102 |
| The basic energy of flow（mJ） | 29.6 | 20.5 |
Embodiment 2
Raw material is equipped with the following proportions：
100 parts of polylactic acid microsphere,
4 parts of graphene oxide,
10 parts of heat stabilizer Ca Zn composite organic matter and ultra-fine hydrotalcite compound,
Antioxidant 2,0.1 part of 6- three-level butyl -4- methylphenols,
0.1 part of defoamer dimethyl polysiloxane,
0.1 part of levelling agent dimethyl silicone polymer.
1）By weight, at room temperature so that under 1000-1400r/min speed conditions, into container, addition is poly- successively
Lactic acid microspheres, graphene oxide, heat stabilizer, antioxidant, defoamer, levelling agent, high-speed stirred 10min~30min are fully mixed
Close；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：
100~120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down and obtained by spray drying exit
High fluidity polylactic acid microsphere is material modified.The main performance of pure polylactic acid microsphere and the polylactic acid microsphere being modified is carried out
Detection, testing result is as follows：
| Detection project | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Impact strength（J/m） | 15 | 39 |
| Heat distortion temperature（℃） | 60 | 93 |
| The basic energy of flow（mJ） | 29.6 | 19.3 |
Embodiment 3
(1) raw material is equipped with the following proportions：
100 parts of polylactic acid microsphere,
5 parts of heat stabilizer Ca Zn composite organic matter and ultra-fine hydrotalcite compound,
5 parts of graphene oxide,
Antioxidant 2,5 parts of 6- three-level butyl -4- methylphenols,
10 parts of defoamer dimethyl polysiloxane,
10 parts of levelling agent dimethyl silicone polymer.
1）By weight, at room temperature so that under 1000-1400r/min speed conditions, into container, addition is poly- successively
Lactic acid microspheres, graphene oxide, heat stabilizer, antioxidant, defoamer, levelling agent, high-speed stirred 10min~30min are fully mixed
Close；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：
100~120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down and obtained by spray drying exit
High fluidity polylactic acid microsphere is material modified.The main performance of pure polylactic acid microsphere and the polylactic acid microsphere being modified is carried out
Detection, testing result is as follows：
| Detection project | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Impact strength（J/m） | 15 | 35 |
| Heat distortion temperature（℃） | 60 | 106 |
| The basic energy of flow（mJ） | 29.6 | 19.8 |
Embodiment 4
(1) raw material is equipped with the following proportions：
100 parts of polylactic acid microsphere,
3 parts of heat stabilizer Ca Zn composite organic matter and ultra-fine hydrotalcite compound,
3.5 parts of graphene oxide,
Antioxidant 2,1 part of 6- three-level butyl -4- methylphenols,
4 parts of defoamer dimethyl polysiloxane,
5 parts of levelling agent dimethyl silicone polymer.
1）By weight, at room temperature so that under 1000-1400r/min speed conditions, into container, addition is poly- successively
Lactic acid microspheres, graphene oxide, heat stabilizer, antioxidant, defoamer, levelling agent, high-speed stirred 10min~30min are fully mixed
Close；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：
100~120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down and obtained by spray drying exit
High fluidity polylactic acid microsphere is material modified.The main performance of pure polylactic acid microsphere and the polylactic acid microsphere being modified is carried out
Detection, testing result is as follows：
| Detection project | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Impact strength（J/m） | 15 | 31 |
| Heat distortion temperature（℃） | 60 | 98 |
| The basic energy of flow（mJ） | 29.6 | 20.2 |
Claims (6)
1. a kind of 3D printing is material modified with polylactic acid microsphere, it is characterised in that the material modified polylactic acid microsphere is powdery
Fluent material, is prepared from by weight by following components：
100 parts of polylactic acid microsphere
3-5 parts of graphene oxide
1~10 part of heat stabilizer
0.1~10 part of antioxidant
0.1~10 part of defoamer
0.1~10 part of levelling agent；
The polylactic acid microsphere is material modified, is prepared from by the following method：
1）By weight, at room temperature under 1000-1400r/min speed conditions, to add PLA successively into container
100 parts of microballoon, 3-5 parts of graphene oxide, 1~10 part of heat stabilizer .1~10 part of antioxidant 0 .1~10 part of defoamer 0,
.1~10 part of levelling agent 0, high-speed stirred 10min~30min is sufficiently mixed；
2）By step 1）Obtained mixture feeding rotating nozzle spray dryer is spray-dried, inlet temperature：100~
120 DEG C, softening is combined polylactic acid microsphere with graphene oxide rapidly, is quickly cooled down by spray drying exit and is obtained high flowing
Property polylactic acid microsphere is material modified.
2. a kind of 3D printing according to claim 1 is material modified with polylactic acid microsphere, it is characterised in that described poly- breast
Sour microballoon molecular weight is more than 100,000 and particle diameter is 5um~15um.
3. a kind of 3D printing according to claim 1 is material modified with polylactic acid microsphere, it is characterised in that described heat is steady
Determine the compound that agent constitutes for Ca Zn composite thing and ultra-fine hydrotalcite, its compound proportioning is calcium salt：Zinc salt：Hydrotalcite=1：1：5,
Hydrotalcite is the white powder of layer structure, and its particle diameter is 10nm~100nm, and specific surface area is 10m2∕ g~30m2∕g。
4. a kind of 3D printing according to claim 1 is material modified with polylactic acid microsphere, it is characterised in that described antioxygen
Agent is 2,6- bis- (three-level butyl) -4- methylphenols, double（3,5- bis-（Three-level butyl）- 4- hydroxybenzyls）Thioether, four (β-(3,
5- bis-（Three-level butyl）- 4- hydroxy phenyls) propionic acid) at least one in pentaerythritol ester.
5. a kind of 3D printing according to claim 1 is material modified with polylactic acid microsphere, it is characterised in that described froth breaking
Agent is at least one in dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone.
6. a kind of 3D printing according to claim 1 is material modified with polylactic acid microsphere, it is characterised in that described levelling
Agent is at least one in organosilicon-epoxide ethane copolymer, organosilicon-epoxide propane copolymer and dimethyl silicone polymer.
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Cited By (1)
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| CN108480622A (en) * | 2018-05-08 | 2018-09-04 | 东南大学 | A kind of magnesium alloy spray printing slurry and preparation method thereof |
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| CN106496983A (en) * | 2016-11-17 | 2017-03-15 | 南宁梦幻三体环保科技有限公司 | A kind of graphene composite material of 3D printing |
| CN107022183B (en) * | 2017-05-18 | 2018-12-07 | 成都新柯力化工科技有限公司 | A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch |
| CN107151429A (en) * | 2017-05-26 | 2017-09-12 | 褚建芬 | It is a kind of for PLA/PBAT/ grapheme materials of 3D printing and preparation method thereof |
| CN107227006A (en) * | 2017-06-20 | 2017-10-03 | 苏州奥宇包装科技有限公司 | A kind of graphene oxide modified polylactic acid composite material and preparation method thereof |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
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Inventor after: Liang Qingjie Inventor after: Li Xiaodong Inventor after: Zou Meifang Inventor after: Huang Cuanwei Inventor after: Qin Kezhi Inventor after: Lan Jie Inventor after: Deng Huiwen Inventor after: Wei Ren Inventor before: Chen Qing Inventor before: Ye Renhai Inventor before: Chen Bing |
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Effective date of registration: 20170619 Address after: 530000 the Guangxi Zhuang Autonomous Region Qingxiu District of Nanning City West Village three group Jinzhou Road, building 11, No. 6 Langxi Applicant after: GUANGXI SANJI TECHNOLOGY CO., LTD. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Applicant before: Chengdu Xinkeli Chemical Sci-Tech Co., Ltd. |
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Application publication date: 20160420 Assignee: Fujian Hui Si 3D Technology Co. Ltd. Assignor: GUANGXI SANJI TECHNOLOGY CO., LTD. Contract record no.: 2017450000032 Denomination of invention: Polylactic acid microspherical modified material for 3D printing and preparation method thereof Granted publication date: 20170714 License type: Exclusive License Record date: 20171031 |
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