CN105504713A - Polylactic acid microspherical modified material for 3D printing and preparation method thereof - Google Patents
Polylactic acid microspherical modified material for 3D printing and preparation method thereof Download PDFInfo
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- CN105504713A CN105504713A CN201511002069.9A CN201511002069A CN105504713A CN 105504713 A CN105504713 A CN 105504713A CN 201511002069 A CN201511002069 A CN 201511002069A CN 105504713 A CN105504713 A CN 105504713A
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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
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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
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Abstract
The invention provides a polylactic acid microspherical modified material for 3D printing. The material is prepared from, by weight, 100 parts of polylactic acid microspheres, 3-5 parts of graphene oxide, 1-10 parts of a heat stabilizer, 0.1-10 parts of an anti-oxidation agent, 0.1-10 parts of a defoaming agent and 0.1-10 parts of a flatting agent. Powder liquidity and heat stability of the material can be remarkably improved by adding a compound composed of graphene oxide, the heat stabilizer calcium-zinc compound and ultra-fine hydrotalcite, the material can be used for 3D printing precise parts, heat stability and toughness of the parts can be remarkably improved, and besides, the material is simple in the production technology, environmentally friendly and free of pollution and can be directly used for 3D printing.
Description
Technical field
The present invention relates to technical field of macromolecules, it is material modified and preparation method thereof with its application in 3D prints to be specifically related to a kind of polylactic acid microsphere.
Background technology
3D printing technique is a kind of based on digital model file, uses powdery metal or plastics etc. can jointing material, is carried out the technology of constructed object by the mode successively printed.Ultimate principle is layered manufacturing, successively increases the technology that material generates 3D solid.At present, 3D printing technique is mainly applied to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes the retrofit technique that these tradition rely on.In addition, 3D printing technique is applied to the fields such as medical science, biotechnology, building, clothes, aviation gradually, for wide space has been opened up in innovation.
Micro polymer ball material, as functional high molecule material, has a wide range of applications in analytical chemistry, biological chemistry and other high-technology fields.Wherein poly(lactic acid) (PLA) microballoon is owing to having fully biodegradable and taking renewable resources as the plant origin of raw material, is described as the most potential biological degradation polyalcohol material, so the research of polylactic acid microsphere technology of preparing is very active.Prepare the known method of polylactic acid microsphere and have emulsification-solidification method, spray-drying process and solvent-nonsolvent method.Wherein the most conventional is emulsification-solidification method, and it implements means is poly(lactic acid) dissolved in organic solvent, under stirring by tensio-active agent by its stable dispersion in aqueous, forms emulsion, along with the volatilization of solvent, and poly(lactic acid) drop solidifying formation gradually.
China Patent Publication No. CN103146164A discloses a kind of poly-lactic acid material nano material toughened for rapid shaping and preparation method thereof, the method utilizes twin screw extruder to carry out blending extrusion modification to polyacrylic acid ester microsphere and poly(lactic acid), although enhance the toughness of poly(lactic acid), but it is not low to the shock strength of poly(lactic acid) and heat-drawn wire is low carries out modification raising, and use twin screw extruder to carry out melt blending modification, cannot microballoon be formed, there is no powder flowbility.Therefore the defect that the heat-drawn wire of polylactic acid microsphere is low, shock strength is low, toughness is bad, the product application scope printed by polylactic acid microsphere is caused to be very restricted, thus, the defect of the application of polylactic acid microsphere in 3D printed material must be overcome by modification.
Polylactic acid microsphere is carried out modification by the present invention, forms the uniform-spherical polylactic acid microsphere of a kind of particle diameter at 10-25um.The preparation method of the polylactic acid microsphere used is shown in China Patent Publication No. CN103172876A, what it adopted is after dissolving poly(lactic acid) and inductor with high boiling solvent, solid-liquid separation is carried out with precipitation agent, and obtain polylactic acid microsphere after drying, what obtain is the polyphosphazene polymer lactic acid microspheres material of a kind of size tunable, good dispersity.
Summary of the invention
Be used for 3D for current polylactic acid microsphere and print the defect that there is poor fluidity, poor heat stability, the invention provides a kind of polylactic acid microsphere material modified, this polylactic acid microsphere is material modified has good powder flowbility and thermostability, can realize 3D powder and print.The preparation method that this polylactic acid microsphere is material modified is provided further, utilize homogenizer, add polylactic acid microsphere successively, graphene oxide, thermo-stabilizer, toughner, oxidation inhibitor, defoamer, flow agent make its high-speed stirring mix, the prepared material modified good fluidity of polylactic acid microsphere, there is excellent thermostability and toughness, production technique is simple, environment friendly and pollution-free, can be directly used in 3D and print.
For achieving the above object, the present invention is by the following technical solutions:
A kind of 3D printing polylactic acid microsphere is material modified, it is characterized in that being prepared from by weight by following component:
Polylactic acid microsphere 100 parts
Graphene oxide 3-5 part
Thermo-stabilizer 1 ~ 10 part
0.1 ~ 10 part, oxidation inhibitor
Defoamer 0.1 ~ 10 part
Flow agent 0.1 ~ 10 part
Described polylactic acid microsphere molecular weight is greater than 100,000 and particle diameter is 5um ~ 15um.
Described thermo-stabilizer is the compound of Ca Zn composite thing and ultra-fine hydrotalcite composition, and its compound proportioning is calcium salt: zinc salt: hydrotalcite=1:1:5, and hydrotalcite is the white powder of laminate structure, and its particle diameter is 10nm ~ 100nm, and specific surface area is 10m
2∕ g
~30m
2∕ g.
Described oxidation inhibitor is at least one in 2,6-, tri-grades of butyl-4-methylphenols, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester.
Described defoamer is at least one in dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone.
Described flow agent is at least one in organosilicon-epoxide ethane multipolymer, organosilicon-epoxide propane multipolymer and polydimethylsiloxane.
The preparation method that polylactic acid microsphere is material modified, is characterized in that preparation method is as follows:
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere 100 parts, graphene oxide 3-5 part, thermo-stabilizer 1 ~ 10 part, 0.1 ~ 10 part, oxidation inhibitor, defoamer 0.1 ~ 10 part, flow agent 0.1 ~ 10 part successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.
The present invention is greater than 100,000 to molecular weight and the polylactic acid microsphere that particle diameter is 5um ~ 15um carries out modification, the compound adding graphene oxide and thermo-stabilizer Ca Zn composite thing and ultra-fine hydrotalcite composition can significantly improve powder flowbility and the thermostability of material, can be used for 3D and print accurate product, significantly can improve thermostability and the toughness of product.
Another object of the present invention is to provide the material modified application in 3D prints of above-mentioned polylactic acid microsphere, and 3D printing technique is more widely used.
Beneficial effect of the present invention has:
1, the present invention adds graphene oxide and thermo-stabilizer, oxidation inhibitor, defoamer and flow agent carry out modification to it in polylactic acid microsphere, and material flowability is good, improves thermostability and the toughness of material simultaneously;
2, the preparation technology that polylactic acid microsphere of the present invention is material modified is simple, environment friendly and pollution-free, low cost of manufacture;
3, the material modified uniform particle sizes of polylactic acid microsphere of the present invention, good fluidity, stable, directly baroque accurate product be can be prepared as through 3D printing device, the thermostability and toughness that print product significantly can be improved.Detect the shock strength printing product according to ASTMD256, the toughness of products adopting the material modified 3D of polylactic acid microsphere of the present invention to print is high, Heat stability is good.
Embodiment
Below in conjunction with specific examples, content of the present invention is further described; but this should be interpreted as scope of the present invention is only limitted to following example, anyly all should belong within the present invention's scope required for protection based on the simple change done by the above-mentioned way of thinking of the present invention or equivalent replacement.If no special instructions, described in each embodiment, number is weight part.
Specific embodiments of the invention are as follows:
Embodiment 1
(1) raw material is equipped with in following ratio:
Polylactic acid microsphere 100 parts,
Thermo-stabilizer Ca Zn composite organism and ultra-fine hydrotalcite compound 1 part,
Graphene oxide 3 parts,
Oxidation inhibitor 2,6-tri-grades of butyl-4-methylphenols 1 part,
Two (3,5-, the tri-grades of butyl-4-hydroxy phenyls) thioether 1 part of oxidation inhibitor,
Defoamer dimethyl polysiloxane 1 part,
Defoamer ethylene oxide propylene oxide copolyether 1 part,
Flow agent organosilicon-epoxide ethane copolymer 1 part,
In flow agent polydimethylsiloxane 1 part.
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere, graphene oxide, thermo-stabilizer, oxidation inhibitor, defoamer, flow agent successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.
The salient features of the polylactic acid microsphere of pure polylactic acid microsphere and modification detected, detected result is as follows:
| Test item | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Shock strength (J/m) | 15 | 36 |
| Heat-drawn wire (DEG C) | 60 | 102 |
| The basic energy of flow (mJ) | 29.6 | 20.5 |
Embodiment 2
Raw material is equipped with in following ratio:
Polylactic acid microsphere 100 parts,
Graphene oxide 4 parts,
Thermo-stabilizer Ca Zn composite organism and ultra-fine hydrotalcite compound 10 parts,
Oxidation inhibitor 2,6-tri-grades of butyl-4-methylphenols 0.1 part,
Defoamer dimethyl polysiloxane 0.1 part,
Flow agent polydimethylsiloxane 0.1 part.
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere, graphene oxide, thermo-stabilizer, oxidation inhibitor, defoamer, flow agent successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.The salient features of the polylactic acid microsphere of pure polylactic acid microsphere and modification detected, detected result is as follows:
| Test item | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Shock strength (J/m) | 15 | 39 |
| Heat-drawn wire (DEG C) | 60 | 93 |
| The basic energy of flow (mJ) | 29.6 | 19.3 |
Embodiment 3
(1) raw material is equipped with in following ratio:
Polylactic acid microsphere 100 parts,
Thermo-stabilizer Ca Zn composite organism and ultra-fine hydrotalcite compound 5 parts,
Graphene oxide 5 parts,
Oxidation inhibitor 2,6-tri-grades of butyl-4-methylphenols 5 parts,
Defoamer dimethyl polysiloxane 10 parts,
Flow agent polydimethylsiloxane 10 parts.
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere, graphene oxide, thermo-stabilizer, oxidation inhibitor, defoamer, flow agent successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.The salient features of the polylactic acid microsphere of pure polylactic acid microsphere and modification detected, detected result is as follows:
| Test item | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Shock strength (J/m) | 15 | 35 |
| Heat-drawn wire (DEG C) | 60 | 106 |
| The basic energy of flow (mJ) | 29.6 | 19.8 |
Embodiment 4
(1) raw material is equipped with in following ratio:
Polylactic acid microsphere 100 parts,
Thermo-stabilizer Ca Zn composite organism and ultra-fine hydrotalcite compound 3 parts,
Graphene oxide 3.5 parts,
Oxidation inhibitor 2,6-tri-grades of butyl-4-methylphenols 1 part,
Defoamer dimethyl polysiloxane 4 parts,
Flow agent polydimethylsiloxane 5 parts.
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere, graphene oxide, thermo-stabilizer, oxidation inhibitor, defoamer, flow agent successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.The salient features of the polylactic acid microsphere of pure polylactic acid microsphere and modification detected, detected result is as follows:
| Test item | Pure polylactic acid microsphere | Polylactic acid microsphere is material modified |
| Shock strength (J/m) | 15 | 31 |
| Heat-drawn wire (DEG C) | 60 | 98 |
| The basic energy of flow (mJ) | 29.6 | 20.2 |
Claims (7)
1. a 3D printing polylactic acid microsphere is material modified, it is characterized in that being prepared from by weight by following component:
Polylactic acid microsphere 100 parts
Graphene oxide 3-5 part
Thermo-stabilizer 1 ~ 10 part
0.1 ~ 10 part, oxidation inhibitor
Defoamer 0.1 ~ 10 part
Flow agent 0.1 ~ 10 part.
2. a kind of 3D printing polylactic acid microsphere according to claim 1 is material modified, it is characterized in that described polylactic acid microsphere molecular weight is greater than 100,000 and particle diameter is 5um ~ 15um.
3. a kind of 3D printing polylactic acid microsphere according to claim 1 is material modified, it is characterized in that described thermo-stabilizer is the compound of Ca Zn composite thing and ultra-fine hydrotalcite composition, its compound proportioning is calcium salt: zinc salt: hydrotalcite=1:1:5, hydrotalcite is the white powder of laminate structure, its particle diameter is 10nm ~ 100nm, and specific surface area is 10m
2∕ g
~30m
2∕ g.
4. a kind of 3D printing polylactic acid microsphere according to claim 1 is material modified, it is characterized in that described oxidation inhibitor is 2,6-tri-grades of butyl-4-methylphenols, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, at least one in four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester.
5. a kind of 3D printing polylactic acid microsphere according to claim 1 is material modified, it is characterized in that described defoamer is at least one in dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone.
6. a kind of 3D printing polylactic acid microsphere according to claim 1 is material modified, it is characterized in that described flow agent is at least one in organosilicon-epoxide ethane multipolymer, organosilicon-epoxide propane multipolymer and polydimethylsiloxane.
7. the preparation method that polylactic acid microsphere is material modified, is characterized in that preparation method is as follows:
1) by weight, at room temperature with under the speed conditions of 1000-1400r/min, in container, add polylactic acid microsphere 100 parts, graphene oxide 3-5 part, thermo-stabilizer 1 ~ 10 part, 0.1 ~ 10 part, oxidation inhibitor, defoamer 0.1 ~ 10 part, flow agent 0.1 ~ 10 part successively, high-speed stirring 10min ~ 30min fully mixes;
2) mixture step 1) obtained is sent into rotating nozzle spray-dryer and is carried out spraying dry, inlet temperature: 100 ~ 120 DEG C, polylactic acid microsphere is softening to be rapidly combined with graphene oxide, is cooled that to obtain high workability polylactic acid microsphere material modified by spray drying exit fast.
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Cited By (5)
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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 |
| CN107022183A (en) * | 2017-05-18 | 2017-08-08 | 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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| CN108480622B (en) * | 2018-05-08 | 2019-10-11 | 东南大学 | A kind of magnesium alloy spray printing slurry and preparation method thereof |
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| 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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| CN105504713B (en) | 2017-07-14 |
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