CN111607255A - Polylactic acid-modified vermiculite composite material, preparation method and application - Google Patents
Polylactic acid-modified vermiculite composite material, preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of polylactic acid composite materials, in particular to a polylactic acid-modified vermiculite composite material, a preparation method and application thereof. Compared with the existing polylactic acid base material, the polylactic acid-modified vermiculite composite material prepared by adopting the modified vermiculite has obviously improved impact strength, heat resistance and crystallization property, and the polylactic acid-modified vermiculite composite material prepared by melting and blending through a screw extruder has small addition amount of the modified vermiculite and obvious effect, so that the polylactic acid-modified vermiculite composite material can be applied to the fields of packaging, building materials and the like, thereby expanding the application field of the polylactic acid material; in addition, the modified vermiculite has important promoting significance for developing high added value of Xinjiang vermiculite resources.
Description
Technical Field
The invention relates to the technical field of polylactic acid composite materials, in particular to a polylactic acid-modified vermiculite composite material and a preparation method thereof, and application of the polylactic acid-modified vermiculite composite material in medical materials, food packaging materials, agricultural film materials or building engineering materials.
Background
Polylactic acid (PLA), a biodegradable material derived from renewable resources, is widely used in various fields, and thus is considered to be a biomedical material and a novel packaging material with the greatest development prospect in the new century. In addition, polylactic acid is also considered as an environmentally friendly material that can replace conventional plastics. However, the defects of slow crystallization rate, high brittleness, low crystallinity, poor heat resistance, poor impact resistance and the like seriously limit the development and application of polylactic acid in the fields of industry, agriculture, biomedicine and the like (Lupeh, Maplegming, Dongfu. polylactic acid modification and application thereof in packaging materials, plastic packaging, 2017(03): 27-36), so that the improvement of the mechanical property, the thermal property and the crystallization property of the polylactic acid by modifying the polylactic acid has important significance. At present, the commonly used modification methods mainly include copolymerization, blending, fiber reinforcement, composite modification and the like to improve the properties of the polylactic acid material such as crystallinity, thermal stability, impact resistance and the like (summer sensitivity, Liujun clever, Wandan courage. environmental friendly polylactic acid modification research progress. engineering plastics application 2014(3): 122-. The method for improving the crystallization rate of the polylactic acid mainly comprises two steps of adding a plasticizer and adding a nucleating agent, and compared with the method for providing heterogeneous nucleation crystal nuclei by adding the nucleating agent to accelerate the crystallization rate of the polylactic acid, the comprehensive performance of the polylactic acid is more effectively and comprehensively improved; in addition, the method of adding the nucleating agent can not only retain the original excellent performances of biodegradability and the like of the polylactic acid, but also endow other functionalities.
Vermiculite (Vermiculite, VMT) is a metamorphic mineral of mafic aluminosilicate with a layered structure having interlaminar water molecules and exchangeable cations. Due to the special structure of vermiculite, the vermiculite has the special properties (Gong Wu, wild goose liter, Zhonna. vermiculite purification process research, proceedings of the institutes of military education, 2009, 19(4): 32-34.) which are not possessed by other materials such as flame retardance, heat insulation, large linear expansion coefficient, small heat conduction coefficient and the like. Therefore, the vermiculite has wide application in the aspects of industry, agriculture, environmental protection, medicine, food and the like, and has higher development and utilization values.
At present, the polylactic acid nucleating agent has rich varieties, but has respective defects: the traditional inorganic nucleating agent has poor compatibility with a polylactic acid matrix; the organic nucleating agent is expensive and has an influence on the environment. Inorganic nucleating agents such as talcum powder, silicon dioxide, montmorillonite and the like have better nucleating property on polylactic acid (Hujun, Dongjie, research progress of nucleating agent on improvement of polylactic acid crystallization. plastics, 2016(3): 108-. In addition to having a structure similar to montmorillonite, vermiculite has better cation exchange capacity, layer expansion capacity, adsorption capacity and good heat preservation and heat insulation performance compared with montmorillonite (senegand, Liu Wentang, He Su celery, Zhu Cheng quan. research progress of polymer/vermiculite composite. engineering plastics application, 2009,37 (2): 84-87.). Compared with montmorillonite, vermiculite has higher net negative charge, excellent low temperature resistance, flame retardant property, sound absorption and other properties (Yachongqing aldehyde resin frogsite nano composite material and application research thereof in brake pads. Master academic thesis of Wuhan university of science & Han Dynasty.2008). In view of the problems of poor compatibility between the inorganic nucleating agent and the PLA matrix, material application limitation and the like, the research on the efficient nucleating agent with strong interface compatibility is a hotspot problem in the research on PLA. Therefore, the surface modification is carried out on the vermiculite by utilizing the structure of the vermiculite, and the polylactic acid nucleating agent with better compatibility and environmental friendliness is developed through amidation modification, so that the method has very important significance for improving the crystallization property of the polylactic acid, promoting the popularization and the use of the polylactic acid, reducing white pollution and the like.
Disclosure of Invention
The invention provides a polylactic acid-modified vermiculite composite material, a preparation method and application thereof, overcomes the defects of the prior art, and can effectively solve the problem that the compatibility of the existing inorganic nucleating agent and a PLA matrix is poor; the problem that the application field of the existing polylactic acid material is limited due to poor toughness, poor heat resistance and low crystallization rate can be solved.
One of the technical schemes of the invention is realized by the following measures: the preparation method of the modified vermiculite comprises the following steps: firstly, taking vermiculite and adding the vermiculite into deionized water to prepare vermiculite suspension; secondly, adding ammonium acetate into the vermiculite suspension, and reacting for 1 to 3 hours at a temperature of between 60 and 80 ℃ to obtain ammonium acetate intercalated vermiculite; and thirdly, adding menaphthylamine, an amide compound, an organic acid and copper bromide into the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 to 13 hours at the temperature of between 160 and 190 ℃, and washing and drying the obtained reaction product to obtain the modified vermiculite.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the amide compound is N, N-dimethylformamide; the organic acid is citric acid; in the second step, the mass ratio of vermiculite to ammonium acetate is 1: 1 to 1: 30.
in the third step, 0.1 to 10 g of menaphthylamine, 5 to 50 ml of N, N-dimethylformamide, 1 to 10 mol of citric acid and 0.1 to 10 mol of copper bromide are added into each gram of the ammonium acetate intercalated vermiculite by taking the ammonium acetate intercalated vermiculite as an adding reference; in the first step, the mass fraction of the vermiculite suspension is 1-10%; and in the third step, the obtained reaction product is sequentially washed by distilled water, filtered, washed by methanol, filtered and dried to obtain the modified vermiculite.
Adding raw vermiculite ore powder into distilled water, stirring into ore pulp with the mass fraction of 15-20%, then adding sodium hexametaphosphate with the mass fraction of 0.3-0.5% into the ore pulp, stirring for 2-5 hours, standing and settling to obtain upper slurry and lower coarse material, centrifugally separating the upper slurry to obtain upper clear liquid and lower slurry, removing the upper clear liquid, and carrying out suction filtration and drying on the lower slurry to obtain the vermiculite.
The second technical scheme of the invention is realized by the following measures: a modified vermiculite is obtained by the following method: firstly, taking vermiculite and adding the vermiculite into deionized water to prepare vermiculite suspension; secondly, adding ammonium acetate into the vermiculite suspension, and reacting for 1 to 3 hours at a temperature of between 60 and 80 ℃ to obtain ammonium acetate intercalated vermiculite; and thirdly, adding menaphthylamine, an amide compound, an organic acid and copper bromide into the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 to 13 hours at the temperature of between 160 and 190 ℃, and washing and drying the obtained reaction product to obtain the modified vermiculite.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the amide compound is N, N-dimethylformamide; the organic acid is citric acid; in the second step, the mass ratio of vermiculite to ammonium acetate is 1: 1 to 1: 30.
in the third step, 0.1 to 10 g of menaphthylamine, 5 to 50 ml of N, N-dimethylformamide, 1 to 10 mol of citric acid and 0.1 to 10 mol of copper bromide are added into each gram of the ammonium acetate intercalated vermiculite by taking the ammonium acetate intercalated vermiculite as an adding reference; in the first step, the mass fraction of the vermiculite suspension is 1-10%; and in the third step, the obtained reaction product is sequentially washed by distilled water, filtered, washed by methanol, filtered and dried to obtain the modified vermiculite.
Adding raw vermiculite ore powder into distilled water, stirring into ore pulp with the mass fraction of 15-20%, then adding sodium hexametaphosphate with the mass fraction of 0.3-0.5% into the ore pulp, stirring for 2-5 hours, standing and settling to obtain upper slurry and lower coarse material, centrifugally separating the upper slurry to obtain upper clear liquid and lower slurry, removing the upper clear liquid, and carrying out suction filtration and drying on the lower slurry to obtain the vermiculite.
The third technical scheme of the invention is realized by the following measures: the polylactic acid-modified vermiculite composite material takes modified vermiculite as a preparation raw material, and the raw material comprises, by weight, 100 parts of polylactic acid resin, 0.05-5 parts of modified vermiculite and 2-10 parts of plasticizer.
The third technical scheme of the invention is further optimized or/and improved as follows:
the polylactic acid-modified vermiculite composite material is obtained by the following method: uniformly mixing the polylactic acid resin, the modified vermiculite and the plasticizer according to the required amount to obtain a mixed raw material, and then extruding the mixed raw material in a screw extruder at the extrusion temperature of 180-200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The plasticizer is more than one of polyethylene glycol, phosphate and acetyl tributyl citrate.
The fourth technical scheme of the invention is realized by the following measures: the polylactic acid-modified vermiculite composite material comprises 100 parts by weight of polylactic acid resin, 0.05 to 5 parts by weight of modified vermiculite and 2 to 10 parts by weight of plasticizer.
The following is further optimization or/and improvement of the fourth technical scheme of the invention:
the plasticizer is more than one of polyethylene glycol, phosphate and acetyl tributyl citrate.
The fifth technical scheme of the invention is realized by the following measures: the polylactic acid-modified vermiculite composite material is applied to medical materials, food packaging materials, agricultural film materials or building engineering materials.
Compared with the existing polylactic acid base material, the polylactic acid-modified vermiculite composite material prepared by adopting the modified vermiculite has obviously improved impact strength, heat resistance and crystallization property, and the polylactic acid-modified vermiculite composite material prepared by melting and blending through a screw extruder has small addition amount of the modified vermiculite and obvious effect, so that the polylactic acid-modified vermiculite composite material can be applied to the fields of packaging, building materials and the like, thereby expanding the application field of the polylactic acid material; in addition, the modified vermiculite has important promoting significance for developing high added value of Xinjiang vermiculite resources.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the modified vermiculite is prepared by the following steps: firstly, adding vermiculite into deionized water, and stirring to obtain a vermiculite suspension with the mass fraction of 1-10%;
secondly, adding ammonium acetate into the vermiculite suspension, wherein the mass ratio of the vermiculite to the ammonium acetate is 1: 1 to 1: 30, reacting for 1 to 3 hours at a temperature of between 60 and 80 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an addition reference, adding 0.1 to 10 g of menaphthylamine, 5 to 50 ml of N, N-dimethylformamide, 1 to 10 mol of citric acid and 0.1 to 10 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing the ammonium acetate intercalated vermiculite, the menaphthylamine, the N, N-dimethylformamide, the citric acid and the copper bromide, reacting for 8 to 13 hours at 160 to 190 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 2: the modified vermiculite is prepared by the following steps: firstly, adding vermiculite into deionized water, and stirring to obtain a vermiculite suspension with the mass fraction of 1-10%;
secondly, adding ammonium acetate into the vermiculite suspension, wherein the mass ratio of the vermiculite to the ammonium acetate is 1: 1 or 1: 30, reacting at 60 ℃ or 80 ℃ for 1 hour or 3 hours to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 0.1 g or 10 g of menaphthylamine, 5 ml or 50 ml of N, N-dimethylformamide, 1 mol or 10 mol of citric acid and 0.1 mol or 10 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing the ammonium acetate intercalated vermiculite, the menaphthylamine, the N, N-dimethylformamide, the citric acid and the copper bromide, reacting for 8 hours or 13 hours at 160 ℃ or 190 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
The modified vermiculite has the advantages of both inorganic mineral nucleating agent and organic amide nucleating agent, the polylactic acid-modified vermiculite composite material is prepared by melting and blending through a screw extruder, the amount of the added modified vermiculite is small, the modification effect is obvious, and the impact strength, the heat resistance and the crystallization performance of the polylactic acid material are improved, so that the polylactic acid-modified vermiculite composite material can be applied to the fields of packaging, building materials and the like, the application field of the polylactic acid material is expanded, and the polylactic acid-modified vermiculite composite material has important promotion significance for the high added value development of Xinjiang vermiculite resources.
Compared with a pure polylactic acid material, the polylactic acid-modified vermiculite composite material prepared from the modified vermiculite obtained by the embodiment of the invention has improved impact strength, thermal decomposition temperature and crystallinity, namely the impact strength, thermal stability and crystallization property of the polylactic acid-modified vermiculite composite material prepared from the modified vermiculite are improved.
Example 3: the vermiculite is obtained by the following method that the raw vermiculite ore powder is added into distilled water and stirred into ore pulp with the mass fraction of 15-20%, then sodium hexametaphosphate with the mass fraction of 0.3-0.5% is added into the ore pulp and stirred for 2-5 hours, standing and settling are carried out to obtain upper layer slurry and lower layer coarse material, the upper layer slurry is centrifugally separated to obtain upper layer clear liquid and lower layer slurry, the upper layer clear liquid is removed, and the lower layer slurry is filtered and dried to obtain the vermiculite.
In addition to the method described in example 3, the vermiculite used in the present invention may be vermiculite obtained by other purification methods known in the art.
Example 4: the polylactic acid-modified vermiculite composite material taking the modified vermiculite as the raw material for preparation in the embodiment comprises 100 parts of polylactic acid resin, 0.05 to 5 parts of modified vermiculite and 2 to 10 parts of plasticizer according to parts by weight, and is obtained by the following method: uniformly mixing the polylactic acid resin, the modified vermiculite and the plasticizer according to the required amount to obtain a mixed raw material, and then extruding the mixed raw material in a screw extruder at the extrusion temperature of 180-200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
Example 5: the polylactic acid-modified vermiculite composite material taking the modified vermiculite as the raw material for preparation in the embodiment comprises 100 parts of polylactic acid resin, 0.05 part or 5 parts of modified vermiculite and 2 parts or 10 parts of plasticizer according to parts by weight, and is obtained by the following method: uniformly mixing the polylactic acid resin, the modified vermiculite and the plasticizer according to the required amount to obtain a mixed raw material, and then extruding the mixed raw material in a screw extruder at the extrusion temperature of 180-200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
Example 6: as the optimization of the above examples 5 and 6, the plasticizer is more than one of polyethylene glycol, phosphate ester and acetyl tributyl citrate.
Example 7: the polylactic acid-modified vermiculite composite material is applied to medical materials, food packaging materials, agricultural film materials or building engineering materials.
Example 8: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.005 kg of modified vermiculite and 0.2 kg of plasticizer (acetyl tributyl citrate) are uniformly mixed to obtain mixed raw materials, and then the mixed raw materials are extruded in a screw extruder at the extrusion temperature of 180 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 8 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain a suspension with the mass fraction of 1%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 1, adding ammonium acetate into the vermiculite suspension, and reacting for 1 hour at 60 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 0.1 g of menaphthylamine, 5 ml of N, N-dimethylformamide, 10 mol of citric acid and 10 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 hours at 160 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
The vermiculite can be obtained by the following method that crushed raw vermiculite ore is taken and added into distilled water to be stirred into ore pulp with the mass fraction of 15-20%, sodium hexametaphosphate solid with the mass fraction of 0.3-0.5% is added into the ore pulp, the mixture is stirred for 2-5 hours, standing and settling are carried out to obtain upper slurry and lower coarse material, the upper slurry is centrifugally separated to obtain upper clear liquid and lower slurry, the upper clear liquid is removed, and the lower slurry is filtered and dried to obtain the vermiculite.
Example 9: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.02 kg of modified vermiculite and 0.4 kg of plasticizer (phosphate and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 185 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 9 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain suspension with the mass fraction of 4%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 5, adding ammonium acetate into the vermiculite suspension, and reacting for 2.5 hours at 63 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 2 g of menaphthylamine, 10 ml of N, N-dimethylformamide, 1 mol of citric acid and 1 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 9 hours at 170 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 10: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.03 kg of modified vermiculite and 0.5 kg of phosphate are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 196 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in this example 10 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain a suspension liquid with the mass fraction of 7%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 17 adding ammonium acetate into the vermiculite suspension, and reacting at 74 ℃ for 1.5 hours to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 7 g of menaphthylamine, 24 ml of N, N-dimethylformamide, 6 mol of citric acid and 2 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 10 hours at 173 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 11: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.04 kg of modified vermiculite and 0.3 kg of (polyethylene glycol, phosphate and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 183 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in this example 11 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain a suspension with the mass fraction of 6%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 23 adding ammonium acetate into the vermiculite suspension, and reacting for 3 hours at 61 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 1 g of menaphthylamine, 30 ml of N, N-dimethylformamide, 4 mol of citric acid and 8 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 9 hours at 187 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 12: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.4 kg of modified vermiculite and 0.7 kg of (polyethylene glycol and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 12 was obtained according to the following preparation method:
firstly, adding vermiculite into deionized water, and stirring to obtain suspension with the mass fraction of 10%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 4, adding ammonium acetate into the vermiculite suspension, and reacting for 1 hour at 70 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 6 g of menaphthylamine, 11 ml of N, N-dimethylformamide, 7 mol of citric acid and 0.5 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 hours at 180 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 13: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.01 kg of modified vermiculite and 0.6 kg of (polyethylene glycol and phosphate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 185 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 13 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain a suspension with the mass fraction of 6%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 11, adding ammonium acetate into the vermiculite suspension, and reacting for 3 hours at 60 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 0.7 g of menaphthylamine, 40 ml of N, N-dimethylformamide, 6 mol of citric acid and 7 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 11 hours at 175 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 14: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.005 kg of modified vermiculite and 0.5 kg of (polyethylene glycol and phosphate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 183 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 14 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain suspension with the mass fraction of 4%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 30 adding ammonium acetate into the vermiculite suspension, and reacting for 2 hours at 65 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 0.7 g of menaphthylamine, 30 ml of N, N-dimethylformamide, 4 mol of citric acid and 7 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 10 hours at 180 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 15: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.4 kg of modified vermiculite and 1.0 kg of (polyethylene glycol and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 15 was obtained according to the following preparation method:
firstly, adding vermiculite into deionized water, and stirring to obtain suspension with the mass fraction of 10%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 28, adding ammonium acetate into the vermiculite suspension, and reacting for 1 hour at 70 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 10 g of menaphthylamine, 11 ml of N, N-dimethylformamide, 7 mol of citric acid and 0.5 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 hours at 180 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 16: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.006 kg of modified vermiculite and 0.5 kg of (polyethylene glycol, phosphate and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 183 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 16 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain a suspension with the mass fraction of 6%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 18, adding ammonium acetate into the vermiculite suspension, and reacting for 2 hours at 75 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 1 g of menaphthylamine, 30 ml of N, N-dimethylformamide, 10 mol of citric acid and 8 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 9 hours at 187 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Example 17: the polylactic acid-modified vermiculite composite material is prepared by the following preparation method: 10 kg of polylactic acid resin, 0.02 kg of modified vermiculite and 0.4 kg of plasticizer (phosphate and acetyl tributyl citrate) are uniformly mixed to obtain a mixed raw material, and then the mixed raw material is extruded in a screw extruder at the extrusion temperature of 185 ℃ to obtain the polylactic acid-modified vermiculite composite material.
The modified vermiculite in example 17 was obtained according to the following preparation method:
step one, adding vermiculite into deionized water, and stirring to obtain suspension with the mass fraction of 4%;
secondly, mixing vermiculite and ammonium acetate according to a mass ratio of 1: 5, adding ammonium acetate into the vermiculite suspension, and reacting for 2.5 hours at 63 ℃ to obtain ammonium acetate intercalated vermiculite;
and thirdly, taking the ammonium acetate intercalated vermiculite as an adding reference, adding 3 g of menaphthylamine, 50 ml of N, N-dimethylformamide, 1 mol of citric acid and 10 mol of copper bromide into each gram of the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 9 hours at 170 ℃, and sequentially washing, filtering, washing with methanol, filtering and drying the obtained reaction product to obtain the modified vermiculite.
Compared with the existing pure polylactic acid material, the polylactic acid-modified vermiculite composite material obtained in the above embodiments 8 to 17 of the invention has obviously improved impact strength, crystallinity and heat resistance; namely, the impact strength of the polylactic acid-modified vermiculite composite material reaches 13.1KJ/m2The final thermal decomposition temperature is 385 ℃ or higher, the maximum thermal decomposition temperature is 362 ℃ or higher, and the crystallinity is 36.32% or higher.
For example, the results of the performance test of the polylactic acid-modified vermiculite composite material obtained in example 8 of the present invention and the existing pure polylactic acid material are described.
The impact strength of the material is tested according to GB/T1043.1-2008, and the impact strength of the polylactic acid-modified vermiculite composite material obtained in the embodiment 8 is 13.1KJ/m2The impact strength of the pure polylactic acid material in the prior art is 9.8kJ/m2(ii) a The crystallinity of the polylactic acid-modified vermiculite composite material obtained in this example 8 is 36.32%, the crystallinity of the pure polylactic acid material in the prior art is 3.82%, and the polylactic acid-modified vermiculite obtained in this example 8The final thermal decomposition temperature of the stone composite material is 385 ℃, and the maximum thermal decomposition temperature is 362 ℃; the final thermal decomposition temperature of the pure polylactic acid material in the prior art is 368 ℃, and the maximum thermal decomposition temperature is 350 ℃. The impact strength and the heat resistance of the polylactic acid-modified vermiculite composite material obtained in the embodiment 8 are obviously improved; meanwhile, the crystallization performance of the polylactic acid-modified vermiculite composite material obtained in the embodiment 8 is improved, so that the application field of the polylactic acid material is expanded.
In conclusion, compared with the existing polylactic acid base material, the polylactic acid-modified vermiculite composite material prepared by adopting the modified vermiculite of the invention has obviously improved impact strength, heat resistance and crystallization property, and the polylactic acid-modified vermiculite composite material prepared by melting and blending through a screw extruder has small addition amount of the modified vermiculite and obvious effect, so that the polylactic acid-modified vermiculite composite material can be applied to the fields of packaging, building materials and the like, thereby expanding the application field of the polylactic acid material; in addition, the modified vermiculite has important promoting significance for developing high added value of Xinjiang vermiculite resources.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (10)
1. The preparation method of the modified vermiculite is characterized by comprising the following steps: firstly, taking vermiculite and adding the vermiculite into deionized water to prepare vermiculite suspension; secondly, adding ammonium acetate into the vermiculite suspension, and reacting for 1 to 3 hours at a temperature of between 60 and 80 ℃ to obtain ammonium acetate intercalated vermiculite; and thirdly, adding menaphthylamine, an amide compound, an organic acid and copper bromide into the ammonium acetate intercalated vermiculite, uniformly mixing, reacting for 8 to 13 hours at the temperature of between 160 and 190 ℃, and washing and drying the obtained reaction product to obtain the modified vermiculite.
2. The method for preparing modified vermiculite according to claim 1, characterized in that the amide compound is N, N-dimethylformamide; or/and the organic acid is citric acid; or/and in the second step, the mass ratio of the vermiculite to the ammonium acetate is 1: 1 to 1: 30.
3. the method for preparing modified vermiculite according to claim 2, characterized in that in the third step, 0.1 to 10 g of menaphthylamine, 5 to 50 ml of N, N-dimethylformamide, 1 to 10 mol of citric acid and 0.1 to 10 mol of copper bromide are added per gram of ammonium acetate intercalated vermiculite; or/and in the first step, the mass fraction of the vermiculite suspension is 1-10%; and in the third step, the obtained reaction product is sequentially washed by distilled water, filtered, washed by methanol, filtered and dried to obtain the modified vermiculite.
4. The preparation method of modified vermiculite according to claim 3, characterized in that the vermiculite is obtained by adding raw vermiculite ore powder into distilled water to prepare ore pulp with mass fraction of 15-20%, then adding sodium hexametaphosphate with mass fraction of 0.3-0.5% into the ore pulp, stirring for 2-5 hours, standing and settling to obtain upper layer slurry and lower layer coarse material, centrifugally separating the upper layer slurry to obtain upper layer clear liquid and lower layer slurry, removing the upper layer clear liquid, filtering and drying the lower layer slurry to obtain the vermiculite.
5. A modified vermiculite obtained by the method of preparing a modified vermiculite according to claim 1 or 2 or 3 or 4.
6. The polylactic acid-modified vermiculite composite material prepared from the modified vermiculite of claim 5 is characterized by comprising 100 parts of polylactic acid resin, 0.05 to 5 parts of modified vermiculite and 2 to 10 parts of plasticizer according to parts by weight.
7. Polylactic acid-modified vermiculite composite according to claim 6, characterized by being obtained by the following process: uniformly mixing the polylactic acid resin, the modified vermiculite and the plasticizer according to the required amount to obtain a mixed raw material, and then extruding the mixed raw material in a screw extruder at the extrusion temperature of 180-200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
8. The polylactic acid-modified vermiculite composite material according to claim 6 or 7, characterized in that the plasticizer is one or more of polyethylene glycol, phosphate ester and acetyl tributyl citrate.
9. A method for preparing polylactic acid-modified vermiculite composite according to claim 6 or 8, characterized in that it is carried out as follows: uniformly mixing the polylactic acid resin, the modified vermiculite and the plasticizer according to the required amount to obtain a mixed raw material, and then extruding the mixed raw material in a screw extruder at the extrusion temperature of 180-200 ℃ to obtain the polylactic acid-modified vermiculite composite material.
10. Use of polylactic acid-modified vermiculite composite material according to claim 6 or 7 or 8 in medical materials or food packaging materials or agricultural film materials or construction engineering materials.
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