CN101475736A - Injection molding method for polylactic acid - Google Patents
Injection molding method for polylactic acid Download PDFInfo
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- CN101475736A CN101475736A CNA2009100450125A CN200910045012A CN101475736A CN 101475736 A CN101475736 A CN 101475736A CN A2009100450125 A CNA2009100450125 A CN A2009100450125A CN 200910045012 A CN200910045012 A CN 200910045012A CN 101475736 A CN101475736 A CN 101475736A
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- lactic acid
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Abstract
The invention belongs to the technical field of polymer materials, and in particular relates to a method for injection of molding polylactic acid. The method comprises the following steps of mixing a nucleating agent into an organic solvent, evenly dispersing the nucleating agent in the solvent under the condition of high-speed stirring, then evenly mixing polylactic acid particles with the weight-average molecular weight of between 60,000 and 200,000, and controlling mass of the nucleating agent to be 0.1 to 10 weight percent of the polylactic acid particles; placing the obtained mixture into a vacuum oven or a rotating drum to remove the organic solvent by evaporating at vacuum or atmospheric pressure and the temperature of between 0 and 80 DEG C; performing low-temperature crystallization on the polylactic acid particles after the organic solvent is evaporated completely in vacuum condition at a temperature of between 80 and 140 DEG C and the crystallinity of not more than 50 percent; and performing direct injection molding on the polylactic acid particles to prepare polylactic acid products. The injection temperature is controlled to be between 140 and 210 DEG C, the mold temperature is controlled to be between 60 and 130 DEG C. The polylactic acid products prepared by the method not only have good heat resistance deformability, and the brittleness is improved, so that the polylactic acid products can be widely applied in general plastic.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of injection molding forming method of poly(lactic acid).
Background technology
Poly(lactic acid) (PLA) is a kind of the have good biocompatibility and polymkeric substance of biodegradable; it derives from renewable resources farm crop (as non-grain crops such as cassava, sweet sorghumes); the most outstanding advantage is a biodegradability; it can be degraded fully by the occurring in nature microorganism after using; final carbonic acid gas and the water of generating; free from environmental pollution, highly beneficial to the protection environment.Poly(lactic acid) has favorable mechanical performance and physicals, is applicable to injection moulding, and is easy to process.But use shortcoming such as poly(lactic acid) exists resistance to heat distorsion poor, and the shrinking percentage of moulded products is big, matter is crisp as engineering plastics.For this reason, both at home and abroad to the thermotolerance that how to improve poly(lactic acid), how to improve aspect such as its toughness and carried out than extensive studies.Wherein, adding crystallization nucleation auxiliary agent raising polymer crystallization speed is a kind of method of using always in polymer modification processing.But traditional blended melting modification method exists crystallization nucleating agent and reunites in polymkeric substance and disperse uneven disadvantage.Patent CN1366004 utilizes twin screw extruder with nucleator and polyester material blend processing, improve the nucleator scattering problem and improved crystallizing polyester speed, but for Biodegradable material, in the processing thermal destruction violent, also reduced molecular weight when improving crystallization velocity.In addition, poly(lactic acid) inherent fragility makes that also polylactic acid article is difficult to moulding, and easily splits frangible.Patent CN1563139 discloses and has a kind ofly prepared the method for poly-lactic acid in high molecular weight by direct condensation, and the poly(lactic acid) limiting viscosity that makes reaches 1.0-1.5dl/g.But the toughness deficiency of poly(lactic acid) homopolymer has limited its application.
Summary of the invention
The object of the present invention is to provide a kind of injection molding forming method of poly(lactic acid), make the polylactic acid article that obtains not only have higher heat-resistant deforming temperature, also have the toughness of obvious improvement.
The injection molding forming method of the poly(lactic acid) that the present invention proposes, concrete steps are as follows:
(1) nucleator is sneaked in the organic solvent, nucleator is dispersed in the organic solvent, be that 6-20 ten thousand poly(lactic acid) particle is evenly sneaked into then with weight-average molecular weight, the quality of control nucleator is the 0.1-10wt% of poly(lactic acid) particle mass;
(2) mixture that step (1) is obtained places vacuum drying oven or rotary drum, and evaporation removes organic solvent under vacuum or normal pressure, and temperature is 0-80 ℃;
(3) treat that organic solvent evaporates fully after, the poly(lactic acid) particle is carried out low crystallization, Tc is 80-140 ℃, degree of crystallinity is no more than 50%;
(4) the poly(lactic acid) particle that step (3) is made directly carries out injection moulding, the preparation polylactic acid article; Wherein, the control injection temperature is 140-210 ℃, and die temperature is 60-130 ℃, and die temperature is preferably 80-110 ℃.
Among the present invention, poly(lactic acid) described in the step (1) be poly-L-lactic acid, poly-D lactic acid, they blend or multipolymer in any.
Among the present invention, nucleator is TiO described in the step (1)
2, CaO, MgO, Al
2O
3, ZnO, SiO
2, talcum powder or CaF
2In any.
Among the present invention, poly(lactic acid) is insoluble to or is slightly soluble in described organic solvent, and the boiling point of described organic solvent is not higher than 100 ℃.Described organic solvent be in methyl alcohol, ethanol or the ethyl acetate any.
The invention has the advantages that:
(1) improves the heat-resistant deforming temperature of polylactic acid article, enlarged the use range of polylactic acid article.
(2) improve the toughness of polylactic acid article, enlarged the use range of polylactic acid article.
(3) directly deal with problems, avoided the loss of molecular weight of polylactic acid modified granulation again in the injection moulding stage.
(4) method is easy, and is with low cost, but widespread use.
Embodiment
Further specify the present invention below by embodiment, helping understanding the present invention, but do not limit content of the present invention.
Embodiment 1:
(1) with 20 gram Al
2O
3Sneaking in 1.2 liters of ethanol, utilize high speed agitator to make and be uniformly dispersed, is that 130,000 poly(lactic acid) particle is evenly sneaked into then with the 1kg weight-average molecular weight;
(2) mixture that step (1) is obtained places vacuum drying oven, and evaporation is 2 hours under 60 ℃ of temperature, the vacuum 1000pa condition;
(3) particle that step (2) is obtained is put into vacuum drum, and crystallization is 1 hour under 95 ℃ of temperature, the vacuum 5000Pa condition, obtains degree of crystallinity and be 38% poly(lactic acid) particle.
(4) the poly(lactic acid) particle that step (3) is made injection moulding under 165 ℃ of injection temperatures, 90 ℃ of conditions of die temperature obtains product.The dimension card heat-drawn wire of products obtained therefrom is 131 ℃.
Embodiment 2:
(1) 15 gram talcum powder being sneaked in 1 liter of methyl alcohol, utilize high speed agitator to make and be uniformly dispersed, is that 140,000 poly(lactic acid) particle is evenly sneaked into then with the 1kg weight-average molecular weight;
(2) mixture that step (1) is obtained places vacuum drying oven, and evaporation is 2 hours under 55 ℃ of temperature, the vacuum 1500pa condition;
(3) particle that step (2) is obtained is put into vacuum drum, and crystallization is 1 hour under 80 ℃ of conditions of temperature, obtains degree of crystallinity and be 31% poly(lactic acid) particle.
(4) the poly(lactic acid) particle that step (3) is made injection moulding under 160 ℃ of injection temperatures, 95 ℃ of conditions of die temperature obtains product.The dimension card heat-drawn wire of products obtained therefrom is 137 ℃.
Embodiment 3:
(1) 80 gram CaO being sneaked in 3 liters of ethanol, utilize high speed agitator to make and be uniformly dispersed, is that 180,000 poly(lactic acid) particle is evenly sneaked into then with the 1kg weight-average molecular weight;
(2) mixture that step (1) is obtained places vacuum drying oven, and evaporation is 3 hours under 70 ℃ of temperature, the vacuum 800pa condition;
(3) particle that step (2) is obtained is put into vacuum drum, and crystallization is 0.5 hour under 120 ℃ of conditions of temperature, obtains degree of crystallinity and be 43% poly(lactic acid) particle.
(4) the poly(lactic acid) particle that step (3) is made injection moulding under 170 ℃ of injection temperatures, 105 ℃ of conditions of die temperature obtains product.The dimension card heat-drawn wire of products obtained therefrom is 128 ℃.
Embodiment 4:
(1) with 30 gram TiO
2Sneaking in 1.5 liters of ethyl acetate, utilize high speed agitator to make and be uniformly dispersed, is that 150,000 poly(lactic acid) particle is evenly sneaked into then with the 1kg weight-average molecular weight;
(2) mixture that step (1) is obtained places vacuum drying oven, and evaporation is 2.5 hours under 65 ℃ of temperature, the vacuum 2000pa condition;
(3) particle that step (2) is obtained is put into vacuum drum, and crystallization is 1 hour under 100 ℃ of conditions of temperature, obtains degree of crystallinity and be 39% poly(lactic acid) particle.
(4) the poly(lactic acid) particle that step (3) is made injection moulding under 165 ℃ of injection temperatures, 90 ℃ of conditions of die temperature obtains product.The dimension card heat-drawn wire of products obtained therefrom is 139 ℃.
The comparative example 1:
With the 1Kg weight-average molecular weight is that 150,000 poly(lactic acid) particle carries out injection moulding, 160 ℃ of injection temperatures, and 30 ℃ of die temperatures, the dimension card heat-drawn wire of products obtained therefrom is 82 ℃.
The comparative example 2:
With the 1Kg weight-average molecular weight is that 130,000 poly(lactic acid) particle carries out injection moulding, 165 ℃ of injection temperatures, and 90 ℃ of die temperatures, the dimension card heat-drawn wire of products obtained therefrom is 101 ℃.
Claims (5)
1. the injection molding forming method of a poly(lactic acid) is characterized in that concrete steps are as follows:
(1) nucleator is sneaked in the organic solvent, nucleator is dispersed in the organic solvent, be that 6-20 ten thousand poly(lactic acid) particle is evenly sneaked into then with weight-average molecular weight, the add-on of control nucleator is the 0.1-10wt% of poly(lactic acid) particle mass;
(2) mixture that step (1) is obtained places vacuum drying oven or rotary drum, and evaporation removes organic solvent under vacuum or normal pressure, and temperature is 0-80 ℃;
(3) treat that organic solvent evaporates fully after, the poly(lactic acid) particle is carried out low crystallization, Tc is 80-140 ℃, degree of crystallinity is no more than 50%;
(4) the poly(lactic acid) particle that step (3) is made directly carries out injection moulding, the preparation polylactic acid article; Wherein, the control injection temperature is 140-210 ℃, and die temperature is 60-130 ℃.
2. the injection molding forming method of poly(lactic acid) according to claim 1 is characterized in that poly(lactic acid) described in the step (1) is poly-L-lactic acid, poly-D lactic acid, their blend or multipolymer.
3. according to claim 1. the injection molding forming method of poly(lactic acid) is characterized in that nucleator is TiO described in the step (1)
2, CaO, MgO, Al
2O
3, ZnO, SiO
2, talcum powder or CaF
2In any.
4. the injection molding forming method of poly(lactic acid) according to claim 1 it is characterized in that poly(lactic acid) is insoluble to or is slightly soluble in described organic solvent, and the boiling point of described organic solvent is not higher than 100 ℃.
5. the injection molding forming method of poly(lactic acid) according to claim 4, it is characterized in that described organic solvent be in methyl alcohol, ethanol or the ethyl acetate any.
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|---|---|---|---|
| CN2009100450125A CN101475736B (en) | 2009-01-08 | 2009-01-08 | Injection molding method for polylactic acid |
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| CN2009100450125A CN101475736B (en) | 2009-01-08 | 2009-01-08 | Injection molding method for polylactic acid |
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| CN101475736B CN101475736B (en) | 2011-01-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476444A (en) * | 2010-11-30 | 2012-05-30 | 远东新世纪股份有限公司 | Method for producing heat resistance polylactic acid component |
| CN102584567A (en) * | 2011-12-29 | 2012-07-18 | 大连理工大学 | Efficient polylactic acid nucleating agent, and preparation method and application thereof |
| CN110218428A (en) * | 2019-07-24 | 2019-09-10 | 建德市康华医疗器材有限公司 | A kind of polylactic acid injected plastics material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100948723B1 (en) * | 2005-05-12 | 2010-03-22 | 미쓰이 가가쿠 가부시키가이샤 | Lactic acid polymer composition, molded article made of same, and method for producing such molded article |
| CN1793228A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing complete biological degradation high flexible polyalctic material |
| CN100478396C (en) * | 2006-04-30 | 2009-04-15 | 东华大学 | Method for improving heat property and crystallization behavior of polylactic acid and its multiple blocked copolymer |
| CN100465229C (en) * | 2006-10-19 | 2009-03-04 | 上海大学 | Process for preparing biologically degradable SiO2/poly lactic acid nano composite material |
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2009
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476444A (en) * | 2010-11-30 | 2012-05-30 | 远东新世纪股份有限公司 | Method for producing heat resistance polylactic acid component |
| CN102476444B (en) * | 2010-11-30 | 2015-06-10 | 远东新世纪股份有限公司 | Method for producing heat resistance polylactic acid component |
| CN102584567A (en) * | 2011-12-29 | 2012-07-18 | 大连理工大学 | Efficient polylactic acid nucleating agent, and preparation method and application thereof |
| CN110218428A (en) * | 2019-07-24 | 2019-09-10 | 建德市康华医疗器材有限公司 | A kind of polylactic acid injected plastics material and preparation method thereof |
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| CN101475736B (en) | 2011-01-19 |
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Assignee: Ma'anshan T-J-L Biomaterials Co., Ltd. Assignor: Shanghai Tong-Jie-Liang Biomaterials Co., Ltd. Contract record no.: 2012340000181 Denomination of invention: Injection molding method for polylactic acid Granted publication date: 20110119 License type: Exclusive License Open date: 20090708 Record date: 20120531 |
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Effective date of registration: 20200420 Address after: No. 2196, South Hongqi Road, Ma'anshan economic and Technological Development Zone, Anhui Province 243000 Patentee after: MAANSHAN TONGJIELIANG BIOLOGICAL MATERIAL Co.,Ltd. Address before: 313 room 65, 200092 Chifeng Road, Shanghai Patentee before: Shanghai Tong-Jie-Liang Biomaterials Co.,Ltd. |
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