聚合物基保鲜包装膜的制备、表征与应用研究
摘要
碳纳米管和分子筛都是具有独特结构和优良性能的多孔无机材料。近年来,碳纳米管和分子筛得到人们的广泛关注,并被广泛用于高分子聚合物基体材料的填充改性,制备各种性能的复合膜。本文把碳纳米管和分子筛分别填充到聚醚砜和聚乙烯的基体中制备复合膜并测定其性能。分子筛-聚乙烯复合膜还用于樱桃的保鲜包装,通过对保鲜效果的考察,探索其用于果蔬保鲜包装膜的可能性。
首先研究碳纳米管和分子筛的纯化修饰。利用混酸(体积比为3∶1浓H2SO4和浓HNO3)纯化修饰碳纳米管以增强其与基体的相容性和分散性。结果表明,碳纳米管在80oC的恒温水浴中冷凝回流4小时后,其红外光谱的吸收峰明显增强增多。通过分析,碳纳米管表面多了很多基团,如-COOH和-OH。分子筛在90oC恒温干燥,去除水分和空气。
其次,采用流延法制备了MCNT含量不同的5种MCNT-聚醚砜复合膜,测定了复合膜的拉伸性能和热重分析。拉伸强度随着MCNT含量的增加而下降。热量峰中,MCNT和聚醚砜的放热峰能独立保留。膜的质量不好,是因为碳纳米管分散地不均匀。
再次,采用吹塑法制备了分子筛含量不同的几种分子筛-聚乙烯复合膜,并测定了复合膜的撕裂、摩擦、拉伸和耐戳穿等性能,还对复合膜进行了X射线衍射、热重分析、红外光谱分析和透光性的研究。结果表明,分子筛和有机聚合物基体的微观结构和性能都能独立地保留。分子筛对复合膜的各种性能都有影响。总体来看,复合膜M3(分子筛含量为7.5%)的性能良好。
最后,利用分子筛-聚乙烯复合膜,对樱桃进行室温保鲜包装研究,通过观察樱桃的外观变化和对失重、折光率、呼吸强度和硬度变化的研究,发现H-β分子筛的加入可以在一定程度上抑制樱桃的呼吸作用,进而延长保鲜期。其中复合膜M3(分子筛含量为7.5%)对新摘樱桃的保鲜效果最好,樱桃的货架寿命可达13天。
Carbon nanotubes and zeolites are both porous inorganic materials with unique structure and excellent performance. Recently, they have been received ever-increasing interests as they have been widely used to modify polymer matrix for fabricating composite membranes of various interests. In this thesis, these two inorganic materials were attempted to fabricate polymer-based composite membranes for goods packaging purpose. Thus the properties of resultant membranes and the fillers themselves were examined and polyethylene-based composite membranes were employed to pack cherries for fresh-keeping practice purpose.
First of all, the purification and modification of carbon nanotubes and zeolites were studied. Mixed acids of sulfuric and nitric acid at a ratio of 3:1 in volume were used to modify multi-walled carbon nanotubes (MCNT) in order to enhance the compatibility with the polymer and improve its dispersion in the matrix. The result shows that, after processed at 80oC in a water bath for 4 hours along with simultaneous reflux condensation, the IR absorption peaks of multi-walled carbon nanotube become stronger and wider. It can be inferred that there are many groups such as -COOH and -OH over the surface of carbon nanotubes after modifications. At 90oC constant temperature, zeolites were dried to remove moisture and gas prior to any property characterizations and subsequent uses.
Five different MCNT-incorporated composite membranes were made by incorporating different loadings of MCNT into polyethersulfone. Our results show the tensile strength declines as the MCNT content increases. The MCNT content is found to have little effect on the weight loss features of the membranes. In the meantime, MCNT and polyethersulfone independently follow their own thermal decomposition behaviors. However, these MCNT-filled composite membranes are not good in quality as carbon nanotube particles can not evenly dispersed in the matrix.
A series of zeolite-incorporated membranes were fabricated by incorporating different amounts of beta zeolite into polyethylene. The tear, friction, stretching, resistance and optical properties of the resultant membranes were examined and the X-ray diffraction, TGA, FTIR analyses were carried out. Experimental results show that, the microstructure and properties of zeolite and organic polymer matrix can be independently reserved. The presence of zeolites has influenced all the physical properties of resultant composite membranes. Over all the composite membranes, the M3 membrane containing 7.5 wt% of zeolite has appreciated integrated property.
Polyethylene-based composite membranes were then used to pack the freshly-harvested cherries for fresh-keeping considerations. The fresh-keeping properties were evaluated by observing the changes in the appearance of cherries and weight loss, refractive index, respiratory strength and hardness. It is found that the addition of H-βzeolites could restrain the respiration rate of cherry, to some extent, and then extend the shelf life. Among the composite membranes, the M3 at zeolite content of 7.5 wt% is the best and the shelf life of cherry can be prolonged up to 13 days.
首先研究碳纳米管和分子筛的纯化修饰。利用混酸(体积比为3∶1浓H2SO4和浓HNO3)纯化修饰碳纳米管以增强其与基体的相容性和分散性。结果表明,碳纳米管在80oC的恒温水浴中冷凝回流4小时后,其红外光谱的吸收峰明显增强增多。通过分析,碳纳米管表面多了很多基团,如-COOH和-OH。分子筛在90oC恒温干燥,去除水分和空气。
其次,采用流延法制备了MCNT含量不同的5种MCNT-聚醚砜复合膜,测定了复合膜的拉伸性能和热重分析。拉伸强度随着MCNT含量的增加而下降。热量峰中,MCNT和聚醚砜的放热峰能独立保留。膜的质量不好,是因为碳纳米管分散地不均匀。
再次,采用吹塑法制备了分子筛含量不同的几种分子筛-聚乙烯复合膜,并测定了复合膜的撕裂、摩擦、拉伸和耐戳穿等性能,还对复合膜进行了X射线衍射、热重分析、红外光谱分析和透光性的研究。结果表明,分子筛和有机聚合物基体的微观结构和性能都能独立地保留。分子筛对复合膜的各种性能都有影响。总体来看,复合膜M3(分子筛含量为7.5%)的性能良好。
最后,利用分子筛-聚乙烯复合膜,对樱桃进行室温保鲜包装研究,通过观察樱桃的外观变化和对失重、折光率、呼吸强度和硬度变化的研究,发现H-β分子筛的加入可以在一定程度上抑制樱桃的呼吸作用,进而延长保鲜期。其中复合膜M3(分子筛含量为7.5%)对新摘樱桃的保鲜效果最好,樱桃的货架寿命可达13天。
Carbon nanotubes and zeolites are both porous inorganic materials with unique structure and excellent performance. Recently, they have been received ever-increasing interests as they have been widely used to modify polymer matrix for fabricating composite membranes of various interests. In this thesis, these two inorganic materials were attempted to fabricate polymer-based composite membranes for goods packaging purpose. Thus the properties of resultant membranes and the fillers themselves were examined and polyethylene-based composite membranes were employed to pack cherries for fresh-keeping practice purpose.
First of all, the purification and modification of carbon nanotubes and zeolites were studied. Mixed acids of sulfuric and nitric acid at a ratio of 3:1 in volume were used to modify multi-walled carbon nanotubes (MCNT) in order to enhance the compatibility with the polymer and improve its dispersion in the matrix. The result shows that, after processed at 80oC in a water bath for 4 hours along with simultaneous reflux condensation, the IR absorption peaks of multi-walled carbon nanotube become stronger and wider. It can be inferred that there are many groups such as -COOH and -OH over the surface of carbon nanotubes after modifications. At 90oC constant temperature, zeolites were dried to remove moisture and gas prior to any property characterizations and subsequent uses.
Five different MCNT-incorporated composite membranes were made by incorporating different loadings of MCNT into polyethersulfone. Our results show the tensile strength declines as the MCNT content increases. The MCNT content is found to have little effect on the weight loss features of the membranes. In the meantime, MCNT and polyethersulfone independently follow their own thermal decomposition behaviors. However, these MCNT-filled composite membranes are not good in quality as carbon nanotube particles can not evenly dispersed in the matrix.
A series of zeolite-incorporated membranes were fabricated by incorporating different amounts of beta zeolite into polyethylene. The tear, friction, stretching, resistance and optical properties of the resultant membranes were examined and the X-ray diffraction, TGA, FTIR analyses were carried out. Experimental results show that, the microstructure and properties of zeolite and organic polymer matrix can be independently reserved. The presence of zeolites has influenced all the physical properties of resultant composite membranes. Over all the composite membranes, the M3 membrane containing 7.5 wt% of zeolite has appreciated integrated property.
Polyethylene-based composite membranes were then used to pack the freshly-harvested cherries for fresh-keeping considerations. The fresh-keeping properties were evaluated by observing the changes in the appearance of cherries and weight loss, refractive index, respiratory strength and hardness. It is found that the addition of H-βzeolites could restrain the respiration rate of cherry, to some extent, and then extend the shelf life. Among the composite membranes, the M3 at zeolite content of 7.5 wt% is the best and the shelf life of cherry can be prolonged up to 13 days.
引文
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