CN115594961B - 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, and belongs to the technical field of polylactic acid modification. The high-toughness heat-resistant polylactic acid composite material is prepared by taking polylactic acid as a matrix, montmorillonite grafted lactide as a filler, polybutylene terephthalate as a toughening agent, and the 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 polylactic acid composite material prepared by the method has lower raw material cost, higher toughness and heat distortion temperature and complete biodegradability, is suitable for the fields of medical treatment, clothing, 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 exhaustion of petroleum resources and various increasingly prominent environmental problems, biodegradable polymer materials have become an extremely important research direction in the field of polymer materials nowadays. Among the biodegradable polymer materials developed at present, polylactic acid is widely applied to the fields of medical treatment and health, food packaging, automobiles, clothing and the like because of the advantages of good biocompatibility, high tensile strength, no toxicity, plastic processing and forming, complete biodegradation and the like. However, the polylactic acid molecular chain segment has high rigidity and poor chain segment movement capability, so that the toughness of the polylactic acid is poor. Meanwhile, the crystallization rate of the polylactic acid is slower, the crystallinity is lower, and the thermal deformation temperature of the polylactic acid is lower. These disadvantages greatly reduce the application value of polylactic acid.
Disclosure of Invention
Aiming at the problems of poor toughness and low heat distortion temperature of the polylactic acid at present, the invention provides a high-toughness heat-resistant polylactic acid composite material and a preparation method thereof, and the prepared polylactic acid composite material has lower raw material cost, larger elongation at break, higher heat distortion temperature and complete biodegradability, is suitable for the fields of medical treatment, clothing, automobiles, food packaging and the like, and has remarkable economic value and social benefit.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high toughness heat resistant polylactic acid composite material is prepared with polylactic acid as matrix, montmorillonite grafted lactide as stuffing, polybutylene terephthalate succinate as toughening agent, and through melt grafting process to prepare glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid as compatilizer and diphenyl dihydrazide sebacate as nucleating agent. The preparation method comprises the following specific steps:
(1) Firstly, adding 30-50 g of polylactic acid into a mixing chamber of a torque rheometer, banburying for 1-3 min at 170-190 ℃, then sequentially adding 2-8 g of glycidyl methacrylate, 4-12 g of butyl methacrylate and 0.1-0.5 g of initiator, continuously banburying for 5-7 min at 160-200 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, 30-50 g of montmorillonite is added into 200-500 mL of dimethyl sulfoxide, mechanical stirring is carried out for 20-40 min at room temperature, 10-30 g of lactide is added, the temperature is raised to 100-140 ℃, mechanical stirring is continued for 30-60 min, then 0.02-0.1 g of catalyst is added, mechanical stirring is continued for 8-12 h, and the montmorillonite grafted lactide is prepared through filtering, washing, drying and grinding;
(3) 15-35 g of polylactic acid, 5-20 g of montmorillonite grafted lactide, 7-20 g of polybutylene terephthalate, 1-9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05-0.25 g of sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 5-10 min at 160-200 ℃, and cooling and crushing are carried out, so that the high-toughness heat-resistant polylactic acid composite material is prepared.
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-dimethylaminopyridine, 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 and polylactic acid, the invention utilizes a melt grafting method to prepare the co-grafted polylactic acid of glycidyl methacrylate and butyl methacrylate, and uses the co-grafted polylactic acid as a compatilizer to improve the compatibility of polybutylene terephthalate and polylactic acid.
(2) Aiming at the problem of poor compatibility of montmorillonite and polylactic acid, the invention grafts lactide capable of reacting with hydroxyl and carboxyl on the surface of the montmorillonite, and the invention improves the compatibility of the montmorillonite and the polylactic acid by the structural advantage that glycidyl methacrylate in the compatilizer can react with lactide on the surface of the montmorillonite and hydroxyl and carboxyl on the surface of the polylactic acid respectively, thereby ensuring that the 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 can be grafted on a polylactic acid molecular chain preferentially and then is subjected to the copolymerization reaction with the glycidyl methacrylate, so that the grafting rate of the glycidyl methacrylate can be improved, and the compatilizer with high grafting rate can improve the compatibility among the components better.
(4) The diphenyl dihydrazide sebacate is a heterogeneous nucleating agent of polylactic acid, can improve the nucleation rate and the nucleation density of the polylactic acid, and achieves the aim of improving the crystallinity and the heat distortion temperature of the polylactic acid. Meanwhile, montmorillonite with high concentration, uniformity and stability in the polylactic acid can also improve the heat distortion temperature of the polylactic acid.
(5) The polylactic acid, the polybutylene terephthalate and the montmorillonite which are used in the invention are all completely biodegradable high polymer materials or natural clay, so that the high-toughness heat-resistant polylactic acid composite material prepared by the invention is environment-friendly and completely biodegradable high polymer materials, meets the national environmental protection concept and meets the requirement of sustainable development.
(6) The polybutylene terephthalate 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 polybutylene terephthalate and the sebacic acid diphenyl dihydrazide can both improve the heat distortion temperature of the polylactic acid composite material, so that the polylactic acid composite material prepared by the invention has lower raw material cost, higher toughness, heat distortion temperature and complete biodegradability, the breaking elongation is 85.3-91.6%, and the impact strength is 6.98-7.65 kJ/m 2 The heat distortion temperature is 67.3-73.5 ℃, is mainly used in the fields of medical treatment, clothing, automobiles and food packaging, and has remarkable economic value and social benefit.
Drawings
FIG. 1 is a chart showing the infrared absorption spectrum of a polylactic acid co-grafted with glycidyl methacrylate and butyl methacrylate, prepared in example 1;
FIG. 2 is an infrared absorption spectrum of montmorillonite grafted lactide prepared in example 1.
Detailed Description
A high-toughness heat-resistant polylactic acid composite material comprises the following specific preparation steps:
(1) Firstly, adding 30-50 g of polylactic acid into a mixing chamber of a torque rheometer, banburying for 1-3 min at 170-190 ℃, then sequentially adding 2-8 g of glycidyl methacrylate, 4-12 g of butyl methacrylate and 0.1-0.5 g of initiator, continuously banburying for 5-7 min at 160-200 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, 30-50 g of montmorillonite is added into 200-500 mL of dimethyl sulfoxide, mechanical stirring is carried out for 20-40 min at room temperature, 10-30 g of lactide is added, the temperature is raised to 100-140 ℃, mechanical stirring is continued for 30-60 min, then 0.02-0.1 g of catalyst is added, mechanical stirring is continued for 8-12 h, and the montmorillonite grafted lactide is prepared through filtering, washing, drying and grinding;
(3) 15-35 g of polylactic acid, 5-20 g of montmorillonite grafted lactide, 7-20 g of polybutylene terephthalate, 1-9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05-0.25 g of sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 5-10 min at 160-200 ℃, and cooling and crushing are carried out, so that the high-toughness heat-resistant polylactic acid composite material is prepared.
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-dimethylaminopyridine, stannous octoate or tri (xylyl) phosphate.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 5 g glycidyl methacrylate, 8 g butyl methacrylate and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, adding 40 g montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(3) 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate, 5 g glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.15 g sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 7 min at 180 ℃, and cooling and crushing are carried out, thus obtaining the high-toughness heat-resistant polylactic acid composite material.
FIG. 1 is a chart showing the infrared absorption spectrum of a polylactic acid co-grafted with glycidyl methacrylate and butyl methacrylate, which is 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 shown to be 910 cm compared with that of the polylactic acid -1 The characteristic absorption peak of the epoxy group at the position shows that the glycidyl methacrylate is successfully grafted with the polylactic acid, and meanwhile, the absorption peak of the epoxy group is positioned at 2997 cm in the infrared absorption spectrum of the polylactic acid co-grafted by the glycidyl methacrylate and the butyl methacrylate -1 Methylene absorption peak at 1749 and 1749 cm -1 The intensity of the carbonyl absorption peak is obviously enhanced, which indicates that the butyl methacrylate is successfully grafted with the polylactic acid.
FIG. 2 is an infrared absorption spectrum of montmorillonite grafted lactide prepared in this example. As can be seen from the figure, compared with the infrared absorption spectrum of montmorillonite, the infrared absorption spectrum of montmorillonite grafted lactide appears to be located at 1749 cm -1 The carbonyl characteristic absorption peak at this point indicates successful grafting of lactide by montmorillonite.
Example 2
(1) Firstly, adding 30 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 3 min at 170 ℃, then sequentially adding 2 g glycidyl methacrylate, 4 g butyl methacrylate and 0.1 g azodiisobutyronitrile, continuously banburying for 7 min at 160 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, 30 g montmorillonite is added into 200 mL dimethyl sulfoxide, mechanical stirring is carried out for 20 min at room temperature, 10 g lactide is added, the temperature is raised to 100 ℃, mechanical stirring is continued for 60 min, then 0.02 g dimethylaminopyridine is added, mechanical stirring is continued for 12 h, and the montmorillonite grafted lactide is prepared through filtration, washing, drying and grinding;
(3) 15 g polylactic acid, 5 g montmorillonite grafted lactide, 7 g polybutylene terephthalate, 1 g glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05 g sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 10 min at 160 ℃, and cooling and crushing are carried out, thus obtaining the high-toughness heat-resistant polylactic acid composite material.
Example 3
(1) Firstly, 50 g polylactic acid is added into a mixing chamber of a torque rheometer, banburying is carried out for 1 min at 190 ℃, then 8 g glycidyl methacrylate, 12 g butyl methacrylate and 0.5 g benzoyl peroxide are sequentially added, banburying is continued for 5 min at 200 ℃, and after cooling and crushing, the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid is prepared;
(2) Under the protection of nitrogen, 50 g montmorillonite is added into 500 mL dimethyl sulfoxide, mechanical stirring is carried out for 40 min at room temperature, then 30 g lactide is added, the temperature is raised to 140 ℃, the mechanical stirring is continued for 30 min, then 0.1 g tri (xylyl) phosphate is added, the mechanical stirring is continued for 8 h, and the montmorillonite grafted lactide is prepared through filtration, washing, drying and grinding;
(3) Sequentially adding 35 g polylactic acid, 20 g montmorillonite grafted lactide, 20 g polybutylene terephthalate, 9 g glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0. 0.25 g sebacic acid diphenyl dihydrazide into a mixing chamber of a torque rheometer, banburying for 5 min at 200 ℃, 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 montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(2) Sequentially adding 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate and 0.15 g diphenyl sebacate 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 2
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 5 g glycidyl methacrylate, 8 g butyl methacrylate and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) 25 g polylactic acid, 12 g montmorillonite, 14 g polybutylene terephthalate, 5 g glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.15 g sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 7 min at 180 ℃, and cooling and crushing are carried out, thus obtaining the finished product.
Comparative example 3
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 5 g glycidyl methacrylate, 8 g butyl methacrylate and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, adding 40 g montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(3) 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate, 5 g glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 7 min at 180 ℃, and cooling and crushing are carried out, thus obtaining the finished product.
Comparative example 4
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 5 g glycidyl methacrylate, 8 g maleic anhydride and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain the glycidyl methacrylate and maleic anhydride co-grafted polylactic acid;
(2) Under the protection of nitrogen, adding 40 g montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(3) 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate, 5 g glycidyl methacrylate and maleic anhydride co-grafted polylactic acid and 0.15 g sebacic acid diphenyl dihydrazide are sequentially added into a mixing chamber of a torque rheometer, banburying is carried out for 7 min at 180 ℃, and cooling and crushing are carried out, thus obtaining the finished product.
Comparative example 5
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 5 g glycidyl methacrylate and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain glycidyl methacrylate grafted polylactic acid;
(2) Under the protection of nitrogen, adding 40 g montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(3) Sequentially adding 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate, 5 g glycidyl methacrylate grafted polylactic acid and 0.15 g 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 6
(1) Firstly, adding 40 g polylactic acid into a mixing chamber of a torque rheometer, banburying for 2 min at 180 ℃, then sequentially adding 8 g butyl methacrylate and 0.3 g dicumyl peroxide, continuously banburying for 6 min at 180 ℃, cooling and crushing to obtain butyl methacrylate grafted polylactic acid;
(2) Under the protection of nitrogen, adding 40 g montmorillonite into 350 mL dimethyl sulfoxide, mechanically stirring for 30 min at room temperature, adding 20 g lactide, heating to 120 ℃, continuously mechanically stirring for 45 min, then adding 0.06 g stannous octoate, continuously mechanically stirring for 10 h, and obtaining montmorillonite grafted lactide through filtering, washing, drying and grinding;
(3) Sequentially adding 25 g polylactic acid, 12 g montmorillonite grafted lactide, 14 g polybutylene terephthalate, 5 g butyl methacrylate grafted polylactic acid and 0.15 g 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.
The products prepared in the examples and comparative examples were tested for tensile strength and elongation at break according to GB/T1040-2006, impact strength according to GB/T1043-2008, heat distortion temperature according to GB/T1634-2019, and the test results are shown in Table 1.
TABLE 1 Performance test results
From the test results, it can be seen that the polylactic acid composite material with higher toughness and heat distortion temperature can be prepared by melt blending with montmorillonite grafted lactide as filler, polybutylene terephthalate as toughening agent, glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid as compatilizer and sebacic acid diphenyl dihydrazide as nucleating agent, and the material cost is lower, the biodegradability is complete, and the application prospect is good.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
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 taking polylactic acid as a matrix, montmorillonite grafted lactide as a filler, polybutylene terephthalate as a toughening agent, and 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) Firstly, banburying 30-50 g of polylactic acid at 170-190 ℃ for 1-3 min, then sequentially adding 2-8 g of glycidyl methacrylate, 4-12 g of butyl methacrylate and 0.1-0.5 g of initiator, continuously banburying at 160-200 ℃ for 5-7 min, cooling and crushing to obtain the glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid;
(2) Under the protection of nitrogen, 30-50 g of montmorillonite is added into 200-500 mL of dimethyl sulfoxide, mechanical stirring is carried out for 20-40 min at room temperature, 10-30 g of lactide is added, the temperature is raised to 100-140 ℃, mechanical stirring is continued for 30-60 min, then 0.02-0.1 g of catalyst is added, mechanical stirring is continued for 8-12 h, and the montmorillonite grafted lactide is prepared through filtering, washing, drying and grinding;
(3) 15-35 g of polylactic acid, 5-20 g of montmorillonite grafted lactide, 7-20 g of polybutylene terephthalate, 1-9 g of glycidyl methacrylate and butyl methacrylate co-grafted polylactic acid and 0.05-0.25 g of sebacic acid diphenyl dihydrazide are sequentially added, banburying is carried out for 5-10 min at 160-200 ℃, and cooling and crushing are carried out, thus obtaining the high-toughness heat-resistant polylactic acid composite material.
2. The method for preparing the high-toughness heat-resistant polylactic acid composite material according to claim 1, wherein the method comprises the following steps: the initiator in the step (1) is any one of azobisisobutyronitrile, dicumyl peroxide or benzoyl peroxide.
3. The method for preparing the high-toughness heat-resistant polylactic acid composite material according to claim 1, wherein the method comprises the following steps: the catalyst in the step (2) is any one of p-dimethylaminopyridine, stannous octoate or tri (xylyl) phosphate.
4. A high toughness heat resistant polylactic acid composite material prepared according to the method of claim 1.
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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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