CN115594961A - High-toughness heat-resistant polylactic acid composite material and preparation method thereof - Google Patents
High-toughness heat-resistant polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-toughness heat-resistant polylactic acid composite material and a preparation method thereof, belonging to the technical field of polylactic acid modification. The high-toughness heat-resistant polylactic acid composite material is prepared by melting and blending polylactic acid serving as a matrix, montmorillonite grafted lactide serving as a filler, polybutylene terephthalate serving as a toughening agent, glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid prepared by a melt grafting method serving as a compatilizer and diphenyl dihydrazide sebacate serving as a nucleating agent. The polylactic acid composite material prepared by the invention has lower raw material cost, higher toughness and thermal deformation temperature and complete biodegradability, is suitable for the fields of medical treatment, clothes, automobiles, food packaging and the like, and has obvious economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of polylactic acid modification, and particularly relates to a high-toughness heat-resistant polylactic acid composite material and a preparation method thereof.
Background
In recent years, with the gradual depletion of petroleum resources and various increasingly outstanding environmental problems, biodegradable polymer materials have become an extremely important research direction in the field of polymer materials nowadays. Among biodegradable polymer materials developed at present, polylactic acid is widely used in the fields of medical care and health, food packaging, automobiles, clothing and the like because of its advantages of good biocompatibility, high tensile strength, no toxicity, plastic processing and molding, complete biodegradation and the like. However, the polylactic acid has a high rigidity of the molecular segment and a low segment mobility, resulting in poor toughness of the polylactic acid. Meanwhile, the crystallization rate of the polylactic acid is slow, and the crystallinity is low, so that the thermal deformation temperature of the polylactic acid is low. These disadvantages greatly reduce the utility value of polylactic acid.
Disclosure of Invention
The invention provides a high-toughness heat-resistant polylactic acid composite material and a preparation method thereof, aiming at the problems of poor toughness and low heat distortion temperature of the existing polylactic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-toughness heat-resistant polylactic acid composite material is prepared by using polylactic acid as a matrix, montmorillonite grafted lactide as a filler, polybutylene terephthalate succinate as a toughening agent, glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid prepared by a melt grafting method as a compatilizer and sebacic acid diphenyl dihydrazide as a nucleating agent through melt blending. The preparation method comprises the following specific steps:
(1) Adding 30-50 g of polylactic acid into a mixing chamber of a torque rheometer, banburying at 170-190 ℃ for 1-3 min, sequentially adding 2-8 g of glycidyl methacrylate, 4-12 g of butyl methacrylate and 0.1-0.5 g of an initiator, banburying at 160-200 ℃ for 5-7 min, cooling, and crushing to obtain co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 30-50 g of montmorillonite into 200-500 mL of dimethyl sulfoxide, mechanically stirring for 20-40 min at room temperature, adding 10-30 g of lactide, heating to 100-140 ℃, continuously mechanically stirring for 30-60 min, then adding 0.02-0.1 g of catalyst, continuously mechanically stirring for 8-12 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Sequentially adding 15 to 35 g of polylactic acid, 5 to 20 g of montmorillonite grafted lactide, 7 to 20 g of polybutylene terephthalate succinate, 1 to 9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05 to 0.25 g of diphenyl dihydrazide sebacate into a mixing chamber of a torque rheometer, carrying out banburying at 160 to 200 ℃ for 5 to 10 min, cooling and crushing to prepare the high-toughness heat-resistant polylactic acid composite material.
Further, the initiator in the step (1) is any one of azobisisobutyronitrile, dicumyl peroxide or benzoyl peroxide.
Further, the catalyst in the step (2) is any one of p-dimethylamino pyridine, stannous octoate or tri (xylyl) phosphate.
Compared with the prior art, the invention has the following advantages:
(1) Aiming at the problem of poor compatibility of polybutylene terephthalate succinate and polylactic acid, the invention prepares the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate by using a melt grafting method, and takes the co-grafted polylactic acid as a compatilizer to improve the compatibility of the polybutylene terephthalate succinate and the polylactic acid.
(2) Aiming at the problem of poor compatibility of montmorillonite and polylactic acid, the invention grafts lactide capable of reacting with polylactic acid terminal hydroxyl and terminal carboxyl on the surface of montmorillonite, and on the other hand, improves the compatibility of montmorillonite and polylactic acid by the structural advantage that glycidyl methacrylate in the compatilizer can respectively react with the lactide on the surface of montmorillonite and the terminal hydroxyl and terminal carboxyl of polylactic acid, and ensures that montmorillonite can be uniformly and stably dispersed in the polylactic acid.
(3) Because the activity of the free radical reaction of the butyl methacrylate and the polylactic acid is greater than that of the free radical reaction of the glycidyl methacrylate and the polylactic acid, and the reaction rate of the copolymerization of the glycidyl methacrylate and the butyl methacrylate is greater than that of the self polymerization of the glycidyl methacrylate, in the preparation of the compatilizer, the butyl methacrylate is preferentially grafted on a polylactic acid molecular chain and then undergoes the copolymerization with the glycidyl methacrylate, so that the grafting rate of the glycidyl methacrylate can be improved, and the compatilizer with high grafting rate can better improve the compatibility among the components.
(4) Sebacic acid diphenyl dihydrazide is a heterogeneous nucleating agent of polylactic acid, and can improve the nucleation rate and the nucleus density of the polylactic acid and achieve the aim of improving the crystallinity and the heat distortion temperature of the polylactic acid. Meanwhile, the montmorillonite with high concentration, uniformity and stable dispersion in the polylactic acid can also improve the thermal deformation temperature of the polylactic acid.
(5) The polylactic acid, the polybutylene terephthalate succinate and the montmorillonite used in the invention are all high polymer materials or natural clay which can be completely biodegraded, so the high-toughness heat-resistant polylactic acid composite material prepared by the invention is an environment-friendly high polymer material which can be completely biodegraded, meets the national environmental protection concept, and meets the sustainable development requirement.
(6) The polybutylene terephthalate succinate can endow the polylactic acid composite material with excellent toughness, the high-content montmorillonite can reduce the raw material cost of the polylactic acid composite material, and the high-content montmorillonite and the sebacic acid diphenyl dihydrazide can improve the heat distortion temperature of the polylactic acid composite material, so that the polylactic acid composite material prepared by the method has the advantages of low raw material cost, high toughness, high heat distortion temperature and capability of completing the heat distortion temperatureThe total biodegradability is that the elongation at break is 85.3 to 91.6 percent, and the impact strength is 6.98 to 7.65 kJ/m 2 The heat distortion temperature is 67.3 to 73.5 ℃, the material is mainly used in the fields of medical treatment, clothes, automobiles and food packaging, and has remarkable economic value and social benefit.
Drawings
FIG. 1 is a chart showing the infrared absorption spectrum of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid prepared in example 1;
FIG. 2 is an infrared absorption spectrum of the montmorillonite-grafted lactide prepared in example 1.
Detailed Description
A high-toughness heat-resistant polylactic acid composite material is specifically prepared by the following steps:
(1) Adding 30-50 g of polylactic acid into a mixing chamber of a torque rheometer, banburying at 170-190 ℃ for 1-3 min, sequentially adding 2-8 g of glycidyl methacrylate, 4-12 g of butyl methacrylate and 0.1-0.5 g of an initiator, banburying at 160-200 ℃ for 5-7 min, cooling, and crushing to obtain co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 30-50 g of montmorillonite into 200-500 mL of dimethyl sulfoxide, mechanically stirring for 20-40 min at room temperature, adding 10-30 g of lactide, heating to 100-140 ℃, continuously mechanically stirring for 30-60 min, then adding 0.02-0.1 g of catalyst, continuously mechanically stirring for 8-12 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Sequentially adding 15 to 35 g of polylactic acid, 5 to 20 g of montmorillonite grafted lactide, 7 to 20 g of polybutylene terephthalate succinate, 1 to 9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05 to 0.25 g of diphenyl dihydrazide sebacate into a mixing chamber of a torque rheometer, carrying out banburying at 160 to 200 ℃ for 5 to 10 min, cooling and crushing to prepare the high-toughness heat-resistant polylactic acid composite material.
Wherein, the initiator in the step (1) is any one of azobisisobutyronitrile, dicumyl peroxide or benzoyl peroxide.
The catalyst in the step (2) is any one of p-dimethylamino pyridine, stannous octoate or tri (xylyl) phosphate.
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 5 g of glycidyl methacrylate, 8 g of butyl methacrylate and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 30 min, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate, 5 g of co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying at 180 ℃ for 7 min, cooling and crushing to obtain the high-toughness heat-resistant polylactic acid composite material.
FIG. 1 is an infrared absorption spectrum of the co-grafted poly (lactic acid) of glycidyl methacrylate and butyl methacrylate prepared in this example. As can be seen from the figure, the infrared absorption spectrum of the polylactic acid co-grafted with glycidyl methacrylate and butyl methacrylate is 910 cm -1 The characteristic absorption peak of the epoxy group shows that the glycidyl methacrylate is successfully grafted with the polylactic acid, and simultaneously, the infrared absorption of the polylactic acid is co-grafted with the glycidyl methacrylate and the butyl methacrylateIn the spectrum, it is located at 2997 cm -1 Has a methylene absorption peak and is located at 1749 cm -1 The intensity of the absorption peak of the carbonyl group is obviously enhanced, which indicates that the butyl methacrylate is successfully grafted with the polylactic acid.
FIG. 2 is the infrared absorption spectrum of the montmorillonite-grafted lactide prepared in this example. As can be seen from the figure, the infrared absorption spectrum of montmorillonite-grafted lactide appeared at 1749 cm in comparison with that of montmorillonite -1 The characteristic absorption peak of carbonyl group indicates that the montmorillonite is successfully grafted with the lactide.
Example 2
(1) Firstly, 30 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 3 min at 170 ℃, then 2 g of glycidyl methacrylate, 4 g of butyl methacrylate and 0.1 g of azobisisobutyronitrile are sequentially added, the mixture is continuously internally mixed for 7 min at 160 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 30 g of montmorillonite into 200 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 20 min, adding 10 g of lactide, heating to 100 ℃, continuously mechanically stirring for 60 min, then adding 0.02 g of dimethylaminopyridine, continuously mechanically stirring for 12 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Sequentially adding 15 g of polylactic acid, 5 g of montmorillonite grafted lactide, 7 g of polybutylene terephthalate succinate, 1 g of co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate and 0.05 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer, banburying at 160 ℃ for 10 min, cooling and crushing to obtain the high-toughness heat-resistant polylactic acid composite material.
Example 3
(1) Firstly, 50 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 1 min at 190 ℃, then 8 g of glycidyl methacrylate, 12 g of butyl methacrylate and 0.5 g of benzoyl peroxide are sequentially added, the mixture is continuously internally mixed for 5 min at 200 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 50 g of montmorillonite into 500 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 40 min, adding 30 g of lactide, heating to 140 ℃, continuously mechanically stirring for 30 min, then adding 0.1 g of tri (xylyl) phosphate, continuously mechanically stirring for 8 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Adding 35 g of polylactic acid, 20 g of montmorillonite grafted lactide, 20 g of polybutylene terephthalate succinate, 9 g of co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate and 0.25 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying at 200 ℃ for 5 min, cooling and crushing to obtain the high-toughness heat-resistant polylactic acid composite material.
Comparative example 1
(1) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 30 min, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(2) Adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying for 7 min at 180 ℃, cooling and crushing to obtain a finished product.
Comparative example 2
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 5 g of glycidyl methacrylate, 8 g of butyl methacrylate and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Adding 25 g of polylactic acid, 12 g of montmorillonite, 14 g of polybutylene terephthalate succinate, 5 g of co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying for 7 min at 180 ℃, cooling and crushing to obtain a finished product.
Comparative example 3
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 5 g of glycidyl methacrylate, 8 g of butyl methacrylate and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 30 min, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate, 5 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid into a mixing chamber of a torque rheometer in sequence, banburying for 7 min at 180 ℃, cooling and crushing to obtain a finished product.
Comparative example 4
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 5 g of glycidyl methacrylate, 8 g of maleic anhydride and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the mixture is cooled and crushed to prepare the co-grafted polylactic acid of glycidyl methacrylate and maleic anhydride;
(2) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Sequentially adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate, 5 g of glycidyl methacrylate and maleic anhydride co-grafted polylactic acid and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer, banburying for 7 min at 180 ℃, cooling and crushing to obtain a finished product.
Comparative example 5
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 5 g of glycidyl methacrylate and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the glycidyl methacrylate grafted polylactic acid is prepared after cooling and crushing;
(2) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring at room temperature for 30 min, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate, 5 g of glycidyl methacrylate grafted polylactic acid and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying at 180 ℃ for 7 min, cooling and crushing to obtain a finished product.
Comparative example 6
(1) Firstly, 40 g of polylactic acid is added into a mixing chamber of a torque rheometer and is internally mixed for 2 min at 180 ℃, then 8 g of butyl methacrylate and 0.3 g of dicumyl peroxide are sequentially added, the mixture is continuously internally mixed for 6 min at 180 ℃, and the butyl methacrylate grafted polylactic acid is prepared after cooling and crushing;
(2) Under the protection of nitrogen, adding 40 g of montmorillonite into 350 mL of dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g of lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g of stannous octoate, continuously mechanically stirring for 10 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Adding 25 g of polylactic acid, 12 g of montmorillonite grafted lactide, 14 g of polybutylene terephthalate succinate, 5 g of butyl methacrylate grafted polylactic acid and 0.15 g of sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer in sequence, banburying at 180 ℃ for 7 min, cooling and crushing to obtain a finished product.
The products prepared in the examples and the comparative examples are tested according to GB/T1040-2006 for tensile strength and elongation at break, GB/T1043-2008 for impact strength and GB/T1634-2019 for heat distortion temperature, and the test results are shown in Table 1.
TABLE 1 Performance test results
The test result shows that the polylactic acid composite material with higher toughness and thermal deformation temperature can be prepared by melt blending by using montmorillonite grafted lactide as a filler, polybutylene terephthalate succinate as a toughening agent, glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid prepared by a melt grafting method as a compatilizer and sebacic acid diphenyl dihydrazide as a nucleating agent, and the polylactic acid composite material has the advantages of lower raw material cost, complete biodegradability and good application prospect.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of a high-toughness heat-resistant polylactic acid composite material is characterized by comprising the following steps: the high-toughness heat-resistant polylactic acid composite material is prepared by melting and blending polylactic acid serving as a matrix, montmorillonite grafted lactide serving as a filler, polybutylene terephthalate serving as a toughening agent, glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid prepared by a melt grafting method serving as a compatilizer and diphenyl dihydrazide sebacate serving as a nucleating agent.
2. The method for preparing the high-toughness heat-resistant polylactic acid composite material according to claim 1, wherein: the preparation method comprises the following specific steps:
(1) Firstly, mixing 30 to 50 g of polylactic acid for 1 to 3 min at the temperature of 170 to 190 ℃, then sequentially adding 2 to 8 g of glycidyl methacrylate, 4 to 12 g of butyl methacrylate and 0.1 to 0.5 g of initiator, continuously mixing for 5 to 7 min at the temperature of 160 to 200 ℃, cooling and crushing to obtain the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate;
(2) Under the protection of nitrogen, adding 30-50 g of montmorillonite into 200-500 mL of dimethyl sulfoxide, mechanically stirring for 20-40 min at room temperature, adding 10-30 g of lactide, heating to 100-140 ℃, continuously mechanically stirring for 30-60 min, then adding 0.02-0.1 g of catalyst, continuously mechanically stirring for 8-12 h, filtering, washing, drying and grinding to obtain montmorillonite grafted lactide;
(3) Sequentially adding 15-35 g of polylactic acid, 5-20 g of montmorillonite grafted lactide, 7-20 g of polybutylene terephthalate succinate, 1-9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05-0.25 g of sebacic acid diphenyl dihydrazide, banburying at 160-200 ℃ for 5-10 min, cooling and crushing to obtain the high-toughness heat-resistant polylactic acid composite material.
3. The method for preparing the high-toughness heat-resistant polylactic acid composite material according to claim 2, wherein: the initiator in the step (1) is any one of azobisisobutyronitrile, dicumyl peroxide or benzoyl peroxide.
4. The method for preparing the high-toughness heat-resistant polylactic acid composite material according to claim 2, wherein: the catalyst in the step (2) is any one of p-dimethylamino pyridine, stannous octoate or tri (xylyl) phosphate.
5. A high toughness heat resistant polylactic acid composite prepared according to the method of claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311622A (en) * | 2011-09-27 | 2012-01-11 | 成都市新津事丰医疗器械有限公司 | Modified polylactic acid material for disposable syringe |
| KR20120117130A (en) * | 2011-04-14 | 2012-10-24 | 삼성토탈 주식회사 | Polylactic acid resin composition |
| CN115322539A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Polylactic acid composite material and preparation method thereof |
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| KR20120117130A (en) * | 2011-04-14 | 2012-10-24 | 삼성토탈 주식회사 | Polylactic acid resin composition |
| CN102311622A (en) * | 2011-09-27 | 2012-01-11 | 成都市新津事丰医疗器械有限公司 | Modified polylactic acid material for disposable syringe |
| CN115322539A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Polylactic acid composite material and preparation method thereof |
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