CN105694401A - Toughened polylactic acid capable of being used for rapid forming and preparation method thereof - Google Patents
Toughened polylactic acid capable of being used for rapid forming and preparation method thereof Download PDFInfo
- Publication number
- CN105694401A CN105694401A CN201610145728.2A CN201610145728A CN105694401A CN 105694401 A CN105694401 A CN 105694401A CN 201610145728 A CN201610145728 A CN 201610145728A CN 105694401 A CN105694401 A CN 105694401A
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- polylactic acid
- toughener
- preparation
- antioxidant
- plasticizing
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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
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses toughened polylactic acid capable of being used for rapid forming and a preparation method thereof. The modified polylactic acid is prepared through the method which includes the steps that polylactic acid and a toughening agent are dried respectively and then fully mixed in proportion, and the toughened modified polylactic acid is obtained after melt blending and extrusion. The modified polylactic acid can overcome the defect that polylactic acid is prone to brittle failure, the transparency and tensile strength of polylactic acid are not affected, the process is simple, implementation is easy, and the toughened polylactic acid is suitable for being used as a 3D printing consumable.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of plasticizing polylactic acid and preparation method thereof, particularly relate to a kind of plasticizing polylactic acid for rapid shaping and preparation method。
Background technology
3D printing technique refers to by continuous print physical layer superposition, successively increases material and generates the technology of 3D solid, different from traditional removal materials processing, is referred to as again increasing material manufacture (AM)。Current 3D printing technique is mainly used in the fields such as product prototype, Making mold, artistic creation and medical apparatus, and 3D printing technique can improve efficiency and the measure of precision of manufacture largely。
PLA(polylactic acid) it is the novel green plastics of a kind of fully biodegradable, not only there is good biocompatibility and biodegradability, its mechanical property can also match in excellence or beauty with the general-purpose plastics such as polypropylene, polystyrene, the techniques such as extrusion, injection moulding, spinning can be adopted to be processed, can be widely applied to the fields such as clothing, packaging, agricultural, automobile, medical and health。Owing to the raw material of PLA comes from the little molecule lactic acid that biological material (Semen Maydis, Maninot esculenta crantz., Caulis Sacchari sinensis etc.) ferments, the theory of recycling economy and sustainable development is more conformed to compared with the general-purpose plastics deriving from petrochemical industry at present, PLA material after using can be degraded to carbon dioxide and water under composting conditions, belongs to typical low-carbon (LC) footprint polymer。
PLA has the features such as nontoxic odorlessness, safety and environmental protection, is the desirable feedstock as 3D printed material。But PLA there is also the shortcomings such as brittle, impact strength is low, therefore to meet the requirement printing high-quality parts, it is necessary to modifiying PLA activeness and quietness。
For these problems, Chinese patent CN101983986B has invented the preparation method of the copolymer-modified plasticizing polylactic acid of a kind of methyl methacrylate-butyl acrylate and has obtained transparent, toughness reinforcing polylactic acid。
A kind of method obtaining plasticizing polylactic acid with polyether polyester and polylactic acid melt blending of patented invention of application number 201310129311.3。
Said method can overcome the fragility of polylactic acid to improve the impact resistance of material, but the constituent content height added affects the biological degradability of polylactic acid or complex process is unfavorable for industrialized production。
For this, the present invention relates to a kind of method preparing plasticizing polylactic acid by the direct blending extrusion of parallel equidirectional two-screw with toughener and polylactic acid, there is the advantage that technique is simple, cost is low。
Summary of the invention
The plasticizing polylactic acid of the rapid shaping of the present invention aims to overcome that the shortcoming of the easy brittle failure of polylactic acid and does not affect the transparency and the tensile strength of polylactic acid, and technique is simply easy to implement, is suitable as 3D printing consumables。
The purpose of the present invention is achieved through the following technical solutions: a kind of plasticizing polylactic acid that can be used for rapid shaping, it is sufficiently mixed in proportion after polylactic acid and toughener are separately dried process, remelted blending extrusion obtains plasticizing polylactic acid, and toughener is ethylene-methyl acrylate-glyceryl methacrylate。
Preferably, the content of ethylene-acrylate-glycidyl methacrylate is 0.5 ~ 5%。
The preparation method of a kind of plasticizing polylactic acid that can be used for rapid shaping, by polylactic acid, toughener, antioxidant and other auxiliary agent melt blending extrusion, pelletize in double screw extruder；Specifically comprising the following steps that of preparation
A, dried polylactic acid and toughener, antioxidant and other auxiliary agent are added mixer it is sufficiently mixed；
B, the material mixed put in double screw extruder charge door, and barrel temperature is 160～200 DEG C, and die head temperature is 175～190 DEG C, and screw speed is 100～250 revs/min, extruding pelletization；
Wherein, calculating according to the mass fraction, raw material consists of:
Polylactic acid 95～99.5 parts；
Toughener 0.5～5 part；
Antioxidant 0.05～0.2 part；
Toughener is ethylene-acrylate-glycidyl methacrylate；
Antioxidant is one or both compositionss in 1010,168；
Other auxiliary agent can comprise lubricant, hydrolysis-resisting agent etc.。
Preferably, double screw extruder draw ratio is 36: 1～44: 1。
In sum, the invention have the advantages that the method preparation technology is simple, with low cost, the plasticizing polylactic acid transparency prepared is good, and product surface glossiness is good。
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment is only used for explaining the present invention, is not intended that limiting the scope of the present invention。
Embodiment 1:
97 parts of polylactic acid and 3 parts of ethylene-acrylate-glycidyl methacrylate are dried 3 ~ 4 hours at 65 DEG C respectively, adds high-speed mixer after drying, be simultaneously introduced 0.1 part of antioxidant 1010, after mixing 3 minutes in high-speed mixer, obtain premix material。Described number is all according to the mass fraction；
Premix material obtained above being put in double screw extruder charge door, barrel temperature is 165～195 DEG C, and die head temperature is 190 DEG C, and screw speed is 200 revs/min, and twin screw draw ratio is 40: 1, extruding pelletization；
The plasticizing polylactic acid tensile strength 62MPa obtained, extension at break 17.5%。
Embodiment 2:
98.5 parts of polylactic acid and 1.5 parts of ethylene-acrylate-glycidyl methacrylate are dried 3 ~ 4 hours at 65 DEG C respectively, adds high-speed mixer after drying, be simultaneously introduced 0.1 part of antioxidant 1010, after mixing 3 minutes in high-speed mixer, obtain premix material。Described number is all according to the mass fraction；
Premix material obtained above being put in double screw extruder charge door, barrel temperature is 165～195 DEG C, and die head temperature is 190 DEG C, and screw speed is 200 revs/min, and twin screw draw ratio is 40: 1, extruding pelletization；
The plasticizing polylactic acid tensile strength 62MPa obtained, extension at break 14.5%。
Comparative example 1:
100 parts of polylactic acid are dried 3 ~ 4 hours at 65 DEG C, adds high-speed mixer after drying, be simultaneously introduced 0.1 part of antioxidant 1010, after mixing 3 minutes in high-speed mixer, obtain premix material。Described number is all according to the mass fraction；
Premix material obtained above being put in double screw extruder charge door, barrel temperature is 165～195 DEG C, and die head temperature is 190 DEG C, and screw speed is 200 revs/min, and twin screw draw ratio is 40: 1, extruding pelletization；
The polylactic acid tensile strength 61MPa obtained, extension at break 3.5%。
Claims (4)
1. the plasticizing polylactic acid that can be used for rapid shaping, it is characterized in that: be sufficiently mixed in proportion after polylactic acid and toughener are separately dried process, remelted blending extrusion obtains plasticizing polylactic acid, and described toughener is ethylene-methyl acrylate-glyceryl methacrylate。
2. a kind of plasticizing polylactic acid that can be used for rapid shaping according to claim 1, it is characterised in that: the content of described ethylene-acrylate-glycidyl methacrylate is 0.5 ~ 5%。
3. the preparation method of the plasticizing polylactic acid that can be used for rapid shaping, it is characterised in that: by polylactic acid, toughener, antioxidant and other auxiliary agent melt blending extrusion, pelletize in double screw extruder；Specifically comprising the following steps that of preparation
A, dried polylactic acid and toughener, antioxidant and other auxiliary agent are added mixer it is sufficiently mixed；
B, the material mixed put in double screw extruder charge door, and barrel temperature is 160～200 DEG C, and die head temperature is 175～190 DEG C, and screw speed is 100～250 revs/min, extruding pelletization；
Wherein, calculating according to the mass fraction, raw material consists of:
Polylactic acid 95～99.5 parts；
Toughener 0.5～5 part；
Antioxidant 0.05～0.2 part；
Toughener is ethylene-acrylate-glycidyl methacrylate；
Antioxidant is one or both compositionss in 1010,168；
Other auxiliary agent can comprise lubricant, hydrolysis-resisting agent etc.。
4. the preparation method of a kind of plasticizing polylactic acid that can be used for rapid shaping according to claim 3, it is characterised in that: described double screw extruder draw ratio is 36: 1～44: 1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610145728.2A CN105694401A (en) | 2016-03-15 | 2016-03-15 | Toughened polylactic acid capable of being used for rapid forming and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610145728.2A CN105694401A (en) | 2016-03-15 | 2016-03-15 | Toughened polylactic acid capable of being used for rapid forming and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN105694401A true CN105694401A (en) | 2016-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610145728.2A Pending CN105694401A (en) | 2016-03-15 | 2016-03-15 | Toughened polylactic acid capable of being used for rapid forming and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832838A (en) * | 2017-03-17 | 2017-06-13 | 金旸（厦门）新材料科技有限公司 | It is a kind of to polish in the 3D printing material and methods for making and using same of metal appearance |
| CN107163194A (en) * | 2017-04-29 | 2017-09-15 | 成都博美实润科技有限公司 | A kind of high-ductility lactic acid composite material and preparation method thereof |
| CN107201014A (en) * | 2017-06-23 | 2017-09-26 | 吉林中粮生化有限公司 | A kind of transparent oil bottle of high content PLA and preparation method thereof |
| CN107236270A (en) * | 2017-07-24 | 2017-10-10 | 南昌航空大学 | A kind of polydactyl acid 3D printing filament material and preparation method |
| WO2017191089A1 (en) * | 2016-05-03 | 2017-11-09 | Total Research & Technology Feluy | 3d-printed pla articles |
| WO2018090801A1 (en) * | 2016-11-16 | 2018-05-24 | 金发科技股份有限公司 | Polylactic acid 3d printing wire rod and preparation method therefor |
| CN108164942A (en) * | 2017-11-30 | 2018-06-15 | 芜湖林电子科技有限公司 | It is a kind of for PLA composite materials of 3D printing and preparation method thereof |
| CN108659482A (en) * | 2017-03-27 | 2018-10-16 | 中国科学院宁波材料技术与工程研究所 | Biological poly furandicarboxylic acid butanediol ester polydactyl acid alloy and its application |
| CN111393860A (en) * | 2020-04-30 | 2020-07-10 | 安徽宏飞钓具有限公司 | Quickly degradable bionic bait for sea fishing and production process thereof |
| CN114891329A (en) * | 2022-05-11 | 2022-08-12 | 南京工业大学 | Preparation method of degradable polylactic acid modified material with high toughness and oriented to fast forming of catering products |
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| US20060263394A1 (en) * | 2005-05-23 | 2006-11-23 | National Institute Of Advanced Industrial Science And Technology | Environmental raw material capable of providing impact resistance, method of producing the same, and moldings |
| JP2007070379A (en) * | 2005-09-02 | 2007-03-22 | National Institute Of Advanced Industrial & Technology | Environmental material and method for producing the same |
| CN101275011A (en) * | 2007-03-29 | 2008-10-01 | 东丽纤维研究所（中国）有限公司 | High-shock-resistance polylactic acid composite material, preparation thereof and use thereof |
| CN101495568A (en) * | 2006-06-16 | 2009-07-29 | 阿克马法国公司 | Poly(lactic acid) composition with improved impact resistance |
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2016
- 2016-03-15 CN CN201610145728.2A patent/CN105694401A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263394A1 (en) * | 2005-05-23 | 2006-11-23 | National Institute Of Advanced Industrial Science And Technology | Environmental raw material capable of providing impact resistance, method of producing the same, and moldings |
| JP2007070379A (en) * | 2005-09-02 | 2007-03-22 | National Institute Of Advanced Industrial & Technology | Environmental material and method for producing the same |
| CN101495568A (en) * | 2006-06-16 | 2009-07-29 | 阿克马法国公司 | Poly(lactic acid) composition with improved impact resistance |
| CN101275011A (en) * | 2007-03-29 | 2008-10-01 | 东丽纤维研究所（中国）有限公司 | High-shock-resistance polylactic acid composite material, preparation thereof and use thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191089A1 (en) * | 2016-05-03 | 2017-11-09 | Total Research & Technology Feluy | 3d-printed pla articles |
| WO2018090801A1 (en) * | 2016-11-16 | 2018-05-24 | 金发科技股份有限公司 | Polylactic acid 3d printing wire rod and preparation method therefor |
| CN106832838A (en) * | 2017-03-17 | 2017-06-13 | 金旸（厦门）新材料科技有限公司 | It is a kind of to polish in the 3D printing material and methods for making and using same of metal appearance |
| CN108659482A (en) * | 2017-03-27 | 2018-10-16 | 中国科学院宁波材料技术与工程研究所 | Biological poly furandicarboxylic acid butanediol ester polydactyl acid alloy and its application |
| CN107163194A (en) * | 2017-04-29 | 2017-09-15 | 成都博美实润科技有限公司 | A kind of high-ductility lactic acid composite material and preparation method thereof |
| CN107201014A (en) * | 2017-06-23 | 2017-09-26 | 吉林中粮生化有限公司 | A kind of transparent oil bottle of high content PLA and preparation method thereof |
| CN107236270A (en) * | 2017-07-24 | 2017-10-10 | 南昌航空大学 | A kind of polydactyl acid 3D printing filament material and preparation method |
| CN108164942A (en) * | 2017-11-30 | 2018-06-15 | 芜湖林电子科技有限公司 | It is a kind of for PLA composite materials of 3D printing and preparation method thereof |
| CN111393860A (en) * | 2020-04-30 | 2020-07-10 | 安徽宏飞钓具有限公司 | Quickly degradable bionic bait for sea fishing and production process thereof |
| CN114891329A (en) * | 2022-05-11 | 2022-08-12 | 南京工业大学 | Preparation method of degradable polylactic acid modified material with high toughness and oriented to fast forming of catering products |
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Application publication date: 20160622 |