CN103421285B - A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof - Google Patents
A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof Download PDFInfo
- Publication number
- CN103421285B CN103421285B CN201310284707.5A CN201310284707A CN103421285B CN 103421285 B CN103421285 B CN 103421285B CN 201310284707 A CN201310284707 A CN 201310284707A CN 103421285 B CN103421285 B CN 103421285B
- Authority
- CN
- China
- Prior art keywords
- poly
- lactic acid
- nucleator
- dextrorotation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid of the present invention and preparation method thereof, belong to processing of high molecular material technology field, carry out as follows: according to a certain percentage Poly-L-lactic acid and dextrorotation poly(lactic acid) are melt extruded granulation by twin screw extruder, extrusion temperature is 160-190 DEG C.Above-mentioned blend is dried, and carries out anneal, described nucleator can be obtained.This nucleation is extruded with industrial rank poly(lactic acid) melt blending in proportion, then blend is carried out injection moulding.The method can make the crystallization rate of poly(lactic acid) significantly promote, and increases its degree of crystallinity, the grain-size of refinement poly(lactic acid), shortens the shaping cycle of poly(lactic acid), improves its dimensional stability and resistance toheat, and improve the mechanical property of polylactic acid article.
Description
Technical field
The present invention is specifically related to a kind of method utilizing novel nucleator to prepare Environment-friendlyheat-resistant heat-resistant polylactic acid material.The invention belongs to processing of high molecular material technology field.
Background technology
Poly(lactic acid) (PLA) is a kind of important lactic acid derivatives, is take lactic acid as the family macromolecule material that monomer obtains through chemosynthesis or biosynthesizing, nontoxic nonirritant, there is excellent biocompatibility, can by biological decomposition and absorption, plasticity-is strong, easy machine-shaping.It is easily by the enzyme katabolism in the multiple-microorganism of occurring in nature or animal and plant body, final formation water and carbonic acid gas, free from environmental pollution, is thus considered to one of the most promising biodegradable macromolecular material.Its maximum advantage is recyclability and degradability.Recyclability makes its production not rely on oil, can not the undue fluctuation with oil price, makes poly(lactic acid) industry have the good capability of sustainable development; Degradability then ensure that poly(lactic acid) is a kind of environment-friendly material, can slow down the white pollution problems that current plastics bring, and therefore the research of polylactic acid article is subject to the extensive concern of type material industrial community.
Although poly-lactic acid material can have good moulding processability, because its crystallization rate is very slow and degree of crystallinity is low, make to have during poly(lactic acid) forming process cycle longer, the shortcoming such as dimensional stability is poor.Therefore, its injection molding art at tensionless winkler foundation and film production field are subject to many limitations, and due to polylactic acid crystal degree low, make its heat resisting temperature only have 60 DEG C.
In order to accelerate the shaping cycle of polylactic acid article, improving its production efficiency, widening its Application Areas.Various nucleator usually for the production process of poly(lactic acid) improve poly(lactic acid) shaping time crystallization rate, the resistance toheat improving goods and dimensional stability.Existing nucleator is mainly divided into two large classes, is inorganic nucleator and organic nucleating agent respectively.Main representative is polynite, talcum powder, titanium dioxide etc., this kind of nucleator and poly(lactic acid) poor compatibility, exists in the polymer and reunites and disperse uneven problem, then can have influence on the transparency and the mechanical property of poly-lactic acid material when addition height.Patent JP1999-106628 use wax as polylactic acid crystal nucleator, but nucleator and poly(lactic acid) consistency bad, easily separate out, cause actual addition to reduce, nucleus is formed insufficient.Patent US6417294, by adding the composite nucleating agents such as aliphatic carboxylic acid amine, aliphatic carboxylate, fatty alcohol and aliphatic carboxylic acid fat in poly(lactic acid) matrix, obtains and has the transparency and crystalline poly-lactic acid products.But because nucleator is the organic compound of small-molecular-weight, easily overflow in poly(lactic acid).Talcum powder is a kind of widely used nucleator, it is that 15%MWHS-T talcum powder is as crystallization nucleating agent (median size 2.75um) that patent JP1997-25345A adds massfraction, add the mustard acid amides that massfraction is 1% again, be greater than 35% by XRD determining goods degree of crystallinity, the flexible chain of less than 130 DEG C is lower than 20min.Recently, patent CN101423625A adopts the phosphorus compound metal-salt with reductive action as the nucleator of polylactic resin rapid crystallization, and its phosphorus compound metal-salt is that one or more in the bony acid compound metal-salt in Asia, ortho phosphorous acid compound metal salt and the Hypophosporous Acid, 50 compound metal salt containing three valent phosphors or phosphorus hydrogen bond mix.This crystallization nucleating agent is while promoting the growth of crystallization, refinement crystalline size, and effect is better, and crystallization velocity is very fast, have stronger anti-oxidant, thermotolerance, resistance to hydrolysis.Patent CN101857715A and patent CN102174250A is crystallization rate and the Tc that nucleator improves poly(lactic acid) with Compositional type bisamide and benzotriazole and derivative thereof respectively, all achieves good effect.In sum, the nucleator that in the past disclosed patent poly(lactic acid) adopts is mostly nondegradable organism, and this declines causing the environment friendly of poly-lactic acid material, and disclosed in this invention is a kind of method of Environment-friendlyheat-resistant heat-resistant polylactic acid material.
Summary of the invention
Object of the present invention in order to overcome the deficiencies in the prior art, adopt the complex compound of Poly-L-lactic acid and dextrorotation poly(lactic acid) be nucleator to accelerate polylactic acid crystal, improve thermotolerance and the moulding processability of poly(lactic acid) further.
The preparation method of a kind of Environment-friendlyheat-resistant heat-resistant polylactic acid of the present invention, is prepared in the steps below: according to a certain percentage Poly-L-lactic acid and dextrorotation poly(lactic acid) are melt extruded granulation by twin screw extruder, and extrusion temperature is 160-190 DEG C; Above-mentioned blend is dried, and carries out anneal, can nucleator be obtained; Extruded with industrial rank poly(lactic acid) melt blending in proportion by this nucleator, then blend is carried out injection moulding, during injection moulding, mould temperature is 40-50 DEG C; The basic components of poly-lactic acid material is as follows: poly(lactic acid) 100 parts, nucleator 0.1-1 weight part.
Wherein said nucleator is made up of the Poly-L-lactic acid of different ratios and dextrorotation poly(lactic acid); It is 1:3-3:1 that the Poly-L-lactic acid of described nucleator and dextrorotation gather newborn usage ratio; The melt temperature of described nucleator is higher than 230 DEG C.
In wherein said annealing treating process process, annealing temperature is 100 DEG C-150 DEG C, and annealing time is 5-40min.
Wherein said Poly-L-lactic acid molecular weight is 40000-100000g/mol, and dextrorotation polylactic acid molecule amount is 40000-100000g/mol; Dextrorotation poly(lactic acid) is multi-arm structure.
Nucleator prepared by the present invention disperses very even, careful in industrial poly(lactic acid) matrix, and the grain-size of thus poly(lactic acid) formation is all very even, and grain-size is all very little.Resistance toheat and the mechanical property of material are all significantly increased.Nucleator of the present invention can make the Tc of poly(lactic acid) improve 20 DEG C-30 DEG C, greatly accelerates its crystallization rate.Instant invention overcomes traditional crystallization nucleating agent and disperse uneven problem in poly(lactic acid) matrix, thus eliminate the negative impact of nucleator reunion to poly-lactic acid material.
Crystallization nucleating agent selected by the present invention and poly(lactic acid) have good consistency, can be uniformly dispersed in poly(lactic acid) matrix, can cause polylactic acid crystal during cooling, improve its Tc and accelerate its crystallization rate.
Compared with prior art, advantage of the present invention is:
(1) the novel nucleator selected by the present invention improves polylactic acid crystal temperature, and its crystallization rate and degree of crystallinity are all largely increased.
(2) the novel nucleator selected by the present invention is the complex compound of Poly-L-lactic acid and dextrorotation poly(lactic acid), from consistency, the nucleator that the present invention is used and poly(lactic acid) have better consistency, thus dispersion evenly, thus add and can have good effect on a small quantity.
(3) the novel nucleator selected by the present invention and poly(lactic acid) matrix have good consistency, therefore can avoid adding because of nucleator the defect causing poly-lactic acid material mechanical properties decrease.
(4) quickly crystallizing polylactic acid novel method provided by the invention, technical process is simple, and processing characteristics is strong, and cost is low, can realize large-scale industrial production.
Embodiment
Describe the present invention below in conjunction with embodiment.
The preparation of two kinds of nucleators
Nucleator 1(NA1) preparation
Be the Poly-L-lactic acid of 60000g/mol and the dextrorotation poly(lactic acid) ratio melt blending in 1:3 by weight-average molecular weight, granulation.Extrusion temperature is as shown in table 1, and screw speed is 200rpm.Granulation product is placed in 110 DEG C of baking ovens and leaves standstill 20min.
Nucleator 2(NA2) preparation
Be the Poly-L-lactic acid of 60000g/mol and the dextrorotation poly(lactic acid) ratio melt blending in 3:1 by weight-average molecular weight, granulation.Extrusion temperature is as shown in table 1, and screw speed is 200rpm.Granulation product is placed in 135 DEG C of baking ovens and leaves standstill 5min.
Table 1 forcing machine each section of temperature distribution
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | Head | |
| Temperature (DEG C) | 110 | 160 | 180 | 190 | 190 | 195 | 190 |
Comparative example and embodiment
Comparative example one: the preparation of pure poly(lactic acid) batten
Vacuum drying semicrystalline poly (l-lactic acid) (weight-average molecular weight 15Wg/mol) 100 parts of extruding pelletizations in twin screw extruder, are then injection molded into GB test bars by poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in table 2
Comparative example two: the preparation of poly(lactic acid)/talcum powder batten
Vacuum drying semicrystalline poly (l-lactic acid) (weight-average molecular weight 15Wg/mol) 100 parts and 5 parts of surface-treated talcum powder extruding pelletization in twin screw extruder, be then injection molded into GB test bars by poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in table 2
Embodiment one: the preparation of poly(lactic acid)/NA1 batten
Vacuum drying semicrystalline poly (l-lactic acid) (weight-average molecular weight 15Wg/mol) 100 parts and 0.1 portion of NA1 nucleator extruding pelletization in twin screw extruder, be then injection molded into GB test bars by poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in table 2.
Embodiment two: the preparation of poly(lactic acid)/NA2 batten
Vacuum drying semicrystalline poly (l-lactic acid) (weight-average molecular weight 15Wg/mol) 100 parts and 1 portion of NA2 nucleator extruding pelletization in twin screw extruder, be then injection molded into GB test bars by poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in table 2.
Table 2 embodiment properties of sample
| Comparative example one | Comparative example two | Embodiment one | Embodiment two | |
| Heat-drawn wire (DEG C) | 60.4 | 68.5 | 78 | 76 |
| Degree of crystallinity (%) | 5.38 | 30.5 | 38.6 | 41.5 |
| Flexible chain (min) | 27(105℃) | 8(110℃) | 1.8(126℃) | 1.4(126℃) |
| Tensile strength (MPa) | 58.94 | 64.21 | 71.7 | 70.6 |
| Elongation at break (%) | 9.6 | 10.2 | 15.6 | 13.5 |
As can be seen from the table, rapid crystallization polylactic acid material prepared by the present invention is compared with pure poly(lactic acid), there is good thermotolerance and mechanical property, especially its rapid crystallization performance significantly shortens the machine-shaping cycle of poly(lactic acid), enhance productivity, reduce production cost, the above-mentioned description to example can understand and apply the invention for the ease of those skilled in the art.Those of ordinary skill in the art can be easy to make various amendment to these embodiments, and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art enlighten according to the present invention, and the improvement make the present invention and amendment all should within protection scope of the present invention.
Claims (1)
1. a preparation method for Environment-friendlyheat-resistant heat-resistant polylactic acid, is characterized in that being prepared in the steps below: according to a certain percentage Poly-L-lactic acid and dextrorotation poly(lactic acid) are melt extruded granulation by twin screw extruder, and extrusion temperature is 160-190 DEG C; Above-mentioned blend is dried, and carries out anneal, can nucleator be obtained; Extruded with industrial rank poly(lactic acid) melt blending in proportion by this nucleator, then blend is carried out injection moulding, during injection moulding, mould temperature is 40-50 DEG C; The basic components of poly-lactic acid material is as follows: poly(lactic acid) 100 parts, nucleator 0.1-1 weight part;
Wherein said nucleator is made up of the Poly-L-lactic acid of different ratios and dextrorotation poly(lactic acid); It is 1:3-3:1 that the Poly-L-lactic acid of described nucleator and dextrorotation gather newborn usage ratio; The melt temperature of described nucleator is higher than 230 DEG C;
In wherein said annealing treating process process, annealing temperature is 100 DEG C-150 DEG C, and annealing time is 5-40min;
Wherein said Poly-L-lactic acid molecular weight is 40000-100000g/mol, and dextrorotation polylactic acid molecule amount is 40000-100000g/mol; Dextrorotation poly(lactic acid) is multi-arm structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310284707.5A CN103421285B (en) | 2013-07-08 | 2013-07-08 | A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310284707.5A CN103421285B (en) | 2013-07-08 | 2013-07-08 | A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103421285A CN103421285A (en) | 2013-12-04 |
| CN103421285B true CN103421285B (en) | 2016-02-24 |
Family
ID=49646691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310284707.5A Expired - Fee Related CN103421285B (en) | 2013-07-08 | 2013-07-08 | A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103421285B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280335B (en) * | 2016-08-25 | 2018-06-29 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material and its dyeing of a kind of easy coloring |
| CN106380804A (en) * | 2016-09-18 | 2017-02-08 | 扬州大学 | Preparation method of high-performance polycaprolactone/polylactic acid blend material |
| CN110628193A (en) * | 2019-10-30 | 2019-12-31 | 蚌埠学院 | Preparation method and device of high-crystallinity heat-resistant polylactic acid |
| CN110760172A (en) * | 2019-11-05 | 2020-02-07 | 蚌埠学院 | Modification method for rapidly crystallizing high-crystallinity polylactic acid |
| CN112778720A (en) * | 2020-04-09 | 2021-05-11 | 合肥恒鑫环保科技有限公司 | High-viscosity PLA (polylactic acid) film |
| CN113429762A (en) * | 2020-12-31 | 2021-09-24 | 广东奇德新材料股份有限公司 | Starch/polylactic acid/PBAT nano composite material and preparation method thereof |
| CN114989584A (en) * | 2022-05-24 | 2022-09-02 | 东华大学 | Preparation method of polylactic acid composite resin and heat-resistant polylactic acid fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201120133A (en) * | 2009-08-28 | 2011-06-16 | Toray Industries | Polylactic acid stereocomplex, producing method thereof and core agent for polylactic acid resin |
-
2013
- 2013-07-08 CN CN201310284707.5A patent/CN103421285B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201120133A (en) * | 2009-08-28 | 2011-06-16 | Toray Industries | Polylactic acid stereocomplex, producing method thereof and core agent for polylactic acid resin |
Non-Patent Citations (1)
| Title |
|---|
| 退火对聚乳酸/多壁碳纳米管复合材料拉伸性能的影响;陈利等;《青岛科技大学学报（自然科学版）》;20110630;第32卷(第3期);第285-290页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103421285A (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103421285B (en) | A kind of Environment-friendlyheat-resistant heat-resistant polylactic acid and preparation method thereof | |
| CN101544813B (en) | Rapid crystallization polylactic acid composite material and preparation method thereof | |
| CN102108196B (en) | Method for preparing polylactic acid degradable material | |
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| CN106519631B (en) | A kind of antibacterial degradable packaging material for food and its preparation | |
| CN103965596B (en) | A kind of biodegradable polylactic acid based composites and application | |
| CN101857715A (en) | Method for quickly crystallizing polylactic acid | |
| CN102174250A (en) | Organic nucleating agent for rapidly crystallizing polylactic acid and rapidly-crystallized polylactic acid resin of organic nucleating agent | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| CN105153659A (en) | Heat resistant polylactic acid composite material and preparation method thereof | |
| WO2020083049A1 (en) | Tps/pla/pbat blend modified biodegradable resin prepared by using chain extender and preparation method therefor | |
| CN101704972A (en) | High luster fast forming polypropylene material and preparation method thereof | |
| CN104177662A (en) | Biodegradable material as well as preparation method and application of biodegradable material | |
| CN106336531A (en) | Modified corn straw granule enhanced PBAT [poly(butyleneadipate-co-terephthalate)] starch composite material and preparation method thereof | |
| CN103396659A (en) | Method for accelerating crystallization of polylactic acid resin | |
| CN104592730A (en) | Polylactic acid/polyester alloy and preparation method thereof | |
| CN105348757B (en) | A kind of polylactic acid antibacterial matrices and its preparation method and application | |
| CN101402756A (en) | Calcium carbonate composite degradation plastic and method of producing the same | |
| CN103589064B (en) | One relatively wide molecular weight distribution HOPP process for preparing resins | |
| CN102584567B (en) | Efficient polylactic acid nucleating agent, and preparation method and application thereof | |
| CN113185824A (en) | Special full-biodegradable high-strength polylactic acid-based injection molding material and preparation method thereof | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| CN113308100B (en) | Biodegradable polylactic acid/lignin composite material, preparation method and application | |
| CN103102661A (en) | Rapid nucleating agent for polylactic resin | |
| CN103601970B (en) | A kind of High-strength transparent plastic barrel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200910 Address after: 100044 b2-02, floor B2, No. 15-10, Zhongguancun Street, Haidian District, Beijing Patentee after: Beijing Huazhe Jingwei Biotechnology Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160224 Termination date: 20210708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |