CN103421285A - Environment-friendly heat-resistant polylactic acid and preparation method thereof - Google Patents
Environment-friendly heat-resistant polylactic acid and preparation method thereof Download PDFInfo
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- CN103421285A CN103421285A CN2013102847075A CN201310284707A CN103421285A CN 103421285 A CN103421285 A CN 103421285A CN 2013102847075 A CN2013102847075 A CN 2013102847075A CN 201310284707 A CN201310284707 A CN 201310284707A CN 103421285 A CN103421285 A CN 103421285A
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Abstract
The invention provides an environment-friendly heat-resistant polylactic acid and a preparation method thereof, and belongs to the field of polymer material processing technology. The preparation method comprises the following steps: performing melt extrusion and pelleting on L-polylactic acid and D-polylactic acid according to a certain proportion by a double-screw extruder with the extrusion temperature of 160-190 DEG C; drying the mixture, and performing annealing treatment on the mixture to obtain a nucleating agent; performing melt blending extrusion on the nucleating agent and industrial polylactic acid proportionally, and performing injection molding on the blend. According to the method, the crystallization rate of the polylactic acid is greatly improved to increase the crystallinity of the polylactic acid, refine the grain size of the polylactic acid, shorten molding cycle of the polylactic acid, improve the dimensional stability and heat resistance of the polylactic acid, and improve the mechanical performance of polylactic acid products.
Description
Technical field
The present invention is specifically related to a kind of method of utilizing novel nucleator to prepare environmental friendliness heat-proof polylactic acid material.The invention belongs to the processing of high molecular material technology field.
Background technology
Poly(lactic acid) (PLA) is a kind of important lactic acid derivatives, is to take the family macromolecule material that lactic acid obtains through chemosynthesis or biosynthesizing as monomer nontoxic nonirritant, there is good biocompatibility, can be by biological decomposition and absorption, plasticity-is strong, easily machine-shaping.It easily, by the enzyme katabolism in the multiple-microorganism of occurring in nature or animal and plant body, finally forms water and carbonic acid gas, free from environmental pollution, thereby is 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 the undue fluctuation with oil price, and make poly(lactic acid) industry that the good capability of sustainable development be arranged; Degradability has guaranteed that poly(lactic acid) is a kind of environment-friendly material, can slow down the white pollution problems that current plastics bring, so 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, long, the shortcoming such as dimensional stability is poor of cycle is arranged while making the poly(lactic acid) forming process.Therefore, it is subject to many limitations in injection moulding field and film production field without stretching, and, because poly(lactic acid) degree of crystallinity is low, makes its heat resisting temperature only have 60 ℃.
In order to accelerate the shaping cycle of polylactic acid article, improve its production efficiency, widen its Application Areas.Crystallization rate when various nucleators usually improve the poly(lactic acid) moulding for the production process of poly(lactic acid), improve resistance toheat and the dimensional stability of goods.Existing nucleator mainly is divided into two large classes, is respectively inorganic nucleator and organic nucleating agent.Main representative is polynite, talcum powder, titanium dioxide etc., and this class nucleator and poly(lactic acid) consistency are poor, in polymkeric substance, exists and reunites and disperse inhomogeneous problem, can have influence on the transparency and the mechanical property of poly-lactic acid material when addition is high.Patent JP1999-106628 is used wax as the poly(lactic acid) crystallization nucleating agent, but nucleator and poly(lactic acid) consistency are bad, easily separate out, and causes actual addition to reduce, and nucleus forms insufficient.Patent US6417294 has the transparency and crystalline poly-lactic acid products by adding the composite nucleating agents such as aliphatic carboxylic acid amine, aliphatic carboxylate, fatty alcohol and aliphatic carboxylic acid fat in the poly(lactic acid) matrix, obtaining.But, due to the organic compound that nucleator is the small molecules amount, in poly(lactic acid), easily overflow.Talcum powder is a kind of widely used nucleator, it is that the 15%MWHS-T talcum powder is as crystallization nucleating agent (median size 2.75um) that patent JP1997-25345A adds massfraction, the mustard acid amides that to add massfraction be 1% again, be greater than flexible chain below 35%, 130 ℃ lower than 20min by XRD determining goods degree of crystallinity.Recently, patent CN101423625A adopts has the nucleator of the phosphorus compound metal-salt of reductive action as the polylactic resin rapid crystallization, and its phosphorus compound metal-salt is one or more mixing in the bony acid compound metal-salt in Asia, ortho phosphorous acid compound metal salt and the Hypophosporous Acid, 50 compound metal salt that contains three valent phosphors or phosphorus hydrogen bond.This crystallization nucleating agent is when 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 are crystallization rate and the Tc that nucleator improves poly(lactic acid) with Compositional type bisamide and benzotriazole and derivative thereof respectively, have all obtained effect preferably.In sum, the nucleator that former disclosed patent poly(lactic acid) adopts is mostly nondegradable organism, and this will cause the environment friendly of poly-lactic acid material to descend, and disclosed in this invention is a kind of method of environmental friendliness heat-proof polylactic acid material.
Summary of the invention
Purpose of the present invention is in order to overcome the deficiencies in the prior art, and adopting the complex compound of Poly-L-lactic acid and dextrorotation poly(lactic acid) is that nucleator is accelerated the poly(lactic acid) crystallization, further improves thermotolerance and the moulding processability of poly(lactic acid).
The preparation method of a kind of environmental friendliness heat-proof 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 to granulation by twin screw extruder, extrusion temperature is 160-190 ℃; Above-mentioned blend is dried, and carry out anneal, can obtain nucleator; This nucleator is extruded with industrial rank poly(lactic acid) melt blending in proportion, then blend is carried out to injection moulding, during injection moulding, the mould temperature is 40-50 ℃; The basic components of poly-lactic acid material is as follows: 100 parts of poly(lactic acid), nucleator 0.1-1 weight part.
Wherein said nucleator is comprised of Poly-L-lactic acid and the dextrorotation poly(lactic acid) of different ratios; The poly-newborn usage ratio of the Poly-L-lactic acid of described nucleator and dextrorotation is 1:3-3:1; The melt temperature of described nucleator is higher than 230 ℃.
In wherein said annealing treating process process, annealing temperature is 100 ℃-150 ℃, 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; The dextrorotation poly(lactic acid) is the multi-arm structure.
The prepared nucleator of the present invention disperses very even, careful in industrial poly(lactic acid) matrix, thereby the grain-size that poly(lactic acid) forms is all very even, and grain-size is all very little.Resistance toheat and the mechanical property of material all are significantly increased.Nucleator of the present invention can make the Tc of poly(lactic acid) improve 20 ℃-30 ℃, greatly accelerates its crystallization rate.The present invention has overcome traditional crystallization nucleating agent and disperseed inhomogeneous problem in the poly(lactic acid) matrix, thereby eliminated nucleator, reunites to the negative impact of poly-lactic acid material.
The crystallization nucleating agent that the present invention is selected and poly(lactic acid) have good consistency, can be uniformly dispersed in the poly(lactic acid) matrix, when cooling, can cause the poly(lactic acid) crystallization, improve its Tc and accelerate its crystallization rate.
Compared with prior art, advantage of the present invention is:
(1) the selected novel nucleator of the present invention improves the poly(lactic acid) Tc, and its crystallization rate and degree of crystallinity all are largely increased.
(2) the selected novel nucleator of 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, thereby dispersion is more even, thereby interpolation can have good effect on a small quantity.
(3) selected novel nucleator and the poly(lactic acid) matrix of the present invention has good consistency, therefore can avoid causing because of adding of nucleator the defect of 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
Below in conjunction with embodiment, describe the present invention.
The preparation of two kinds of nucleators
Nucleator 1(NA1) preparation
The Poly-L-lactic acid that is 60000g/mol by weight-average molecular weight and dextrorotation poly(lactic acid) are in the ratio melt blending of 1:3, granulation.Extrusion temperature is as shown in table 1, and screw speed is 200rpm.Granulation product is placed in to 110 ℃ of standing 20min. of baking oven
Nucleator 2(NA2) preparation
The Poly-L-lactic acid that is 60000g/mol by weight-average molecular weight and dextrorotation poly(lactic acid) are in the ratio melt blending of 3:1, granulation.Extrusion temperature is as shown in table 1, and screw speed is 200rpm.Granulation product is placed in to 135 ℃ of standing 5min. of baking oven
Each section temperature distribution of table 1 forcing machine
| ? | One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | Head |
| Temperature (℃) | 110 | 160 | 180 | 190 | 190 | 195 | 190 |
Comparative Examples and embodiment
Comparative Examples one: the preparation of pure poly(lactic acid) batten
100 parts of extruding pelletizations in twin screw extruder of vacuum drying half hitch crystal formation poly (l-lactic acid) (weight-average molecular weight 15W g/mol), then be injection molded into the GB test bars by the poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in Table 2
Comparative Examples two: the preparation of poly(lactic acid)/talcum powder batten
100 parts of vacuum drying half hitch crystal formation poly (l-lactic acid)s (weight-average molecular weight 15W g/mol) and 5 parts of surface-treated talcum powder extruding pelletization in twin screw extruder, then be injection molded into the GB test bars by the poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in Table 2
Embodiment mono-: the preparation of poly(lactic acid)/NA1 batten
100 parts of vacuum drying half hitch crystal formation poly (l-lactic acid)s (weight-average molecular weight 15W g/mol) and 0.1 portion of NA1 nucleator extruding pelletization in twin screw extruder, then be injection molded into the GB test bars by the poly(lactic acid) particle, to be measured.Its crystallization rate, heat-drawn wire and mechanical property are in Table 2.
Embodiment bis-: the preparation of poly(lactic acid)/NA2 batten
100 parts of vacuum drying half hitch crystal formation poly (l-lactic acid)s (weight-average molecular weight 15W g/mol) and 1 portion of NA2 nucleator extruding pelletization in twin screw extruder, then be injection molded into the GB test bars by the 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 Examples one | Comparative Examples two | Embodiment mono- | Embodiment bis- |
| Heat-drawn wire (℃) | 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, the prepared rapid crystallization polylactic acid material of 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 costs, the above-mentioned description to example is 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 these embodiments are made to various modifications, and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art enlighten according to the present invention, and the improvement that the present invention is made and modification all should be within protection scope of the present invention.
Claims (4)
1. the preparation method of an environmental friendliness heat-proof polylactic acid, it 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 to granulation by twin screw extruder, extrusion temperature is 160-190 ℃; Above-mentioned blend is dried, and carry out anneal, can obtain nucleator; This nucleator is extruded with industrial rank poly(lactic acid) melt blending in proportion, then blend is carried out to injection moulding, during injection moulding, the mould temperature is 40-50 ℃; The basic components of poly-lactic acid material is as follows: 100 parts of poly(lactic acid), nucleator 0.1-1 weight part.
2. the preparation method of a kind of environmental friendliness heat-proof polylactic acid according to claim 1, is characterized in that wherein said nucleator is comprised of Poly-L-lactic acid and the dextrorotation poly(lactic acid) of different ratios; The poly-newborn usage ratio of the Poly-L-lactic acid of described nucleator and dextrorotation is 1:3-3:1; The melt temperature of described nucleator is higher than 230 ℃.
3. the preparation method of a kind of environmental friendliness heat-proof polylactic acid according to claim 1, is characterized in that in wherein said annealing treating process process, annealing temperature is 100 ℃-150 ℃, and annealing time is 5-40min.
4. the preparation method of a kind of environmental friendliness heat-proof polylactic acid according to claim 1, is characterized in that wherein said Poly-L-lactic acid molecular weight is 40000-100000 g/mol, and dextrorotation polylactic acid molecule amount is 40000-100000 g/mol; The dextrorotation poly(lactic acid) is the multi-arm structure.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280335A (en) * | 2016-08-25 | 2017-01-04 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material of a kind of easy coloring and dyeing thereof |
| 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 |
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| TW201120133A (en) * | 2009-08-28 | 2011-06-16 | Toray Industries | Polylactic acid stereocomplex, producing method thereof and core agent for polylactic acid resin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280335A (en) * | 2016-08-25 | 2017-01-04 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material of a kind of easy coloring and dyeing thereof |
| 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 |
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