【作者】 刘文波；

【导师】 宋湛谦； 于钢；

【作者基本信息】 东北林业大学 ， 林产化学加工工程， 2005， 博士

【摘要】 本文提出超细胶囊概念,并阐述了超细胶囊制备方法、应用领域、技术进展,综述壳聚糖的结构、性能,分析壳聚糖制备胶囊的可行性及制备意义,从而提出以壳聚糖为主要壁材,以维生素E（V_E）、Crystal Violet Lactone结晶紫内酯溶液（CVL）、纳米TiO₂为芯材,采取单凝聚法和复合凝聚法制备超细胶囊的研究方案。研究成囊乳化过程、固化过程、壁材浓度、壁材比例、芯壁比、胶囊干燥温度等工艺条件,找出最佳制备超细胶囊方案。采用激光粒度仪、扫描电子显微镜、傅立叶红外光谱仪、高效液相色谱（HPLC）等检测仪器与分析手段对胶囊性能、成囊机理等进行表征、测试和分析。 以壳聚糖为壁材,V_E为芯材,单凝聚法制备超细胶囊,壳聚糖脱乙酰度大于85%,分子量9×10⁵左右为宜,溶液浓度1.0%,芯壁比1∶1,乳化剂用量6.0%,乳化搅拌速度9000～10000r/min。对胶囊性能表征、测试和分析得到:胶囊粒度小于3μm、粒度分布均一性好,形貌基本为球形;芯材V_E包埋率86.1%;胶囊耐热强度、稳定性良好。胶囊在粒度大小、均一性及芯材包埋率等方面达到国内外凝聚法制备胶囊的先进水平。 以壳聚糖一海藻酸钠为壁材,CVL为芯材,复合凝聚法制备超细胶囊,壁材比例1∶1,壁材浓度均为1.0%,乳化剂用量6.0%,乳化时间30min,固化剂用量10ml,固化时间1h。对胶囊性能表征、测试和分析得到:胶囊粒度在3pm以下、粒度分布均一性好;芯材包埋率达到82.6%。胶囊耐热强度、稳定性、芯材包埋率等性能达到天然材料复合凝聚法制备胶囊的先进水平。 以壳聚糖为壁材,纳米TiO₂为芯材,单凝聚法制备超细胶囊,最佳芯壁比1∶1～1.6∶1,纳米TiO₂直接超声波分散到壁材溶液中,分散效果良好,有利于壳聚糖包埋或其吸附于胶囊表面。对胶囊性能表征、测试和分析得到:胶囊粒度在2μm以下,粒度分布均一性好;胶囊获得良好有机相分散性;胶囊紫外线吸收性能略高于纳米TiO₂、紫外一可见光反射性能与纳米TiO₂相当,并应用于化妆品中。 研究得出,壳聚糖—V_E超细胶囊、壳聚糖—纳米TiO₂超细胶囊加入到化妆品中,化妆品各种感官及理化指标都达到国家标准。通过测试和分析,化妆品中加入壳聚糖—V_E超细胶囊15天后V_E含量下降8.7%,直接加入V_E15天后V_E含量下降22.3%,V_E超细胶囊具有保护和隔离V_E作用;化妆品中加入壳聚糖—纳米TiO₂超细胶囊,纳米TiO₂超细胶囊在化妆品中得到良好分散、没有絮聚,与有机相互溶性良好,化妆品紫外—可见光反射性能与直接加入纳米TiO₂没有明显差别。以壳聚糖—海藻酸钠—CVL超细胶囊为染料,制备无碳复写纸CB纸,其性能指标达到国内同类产品先进水平。 壳聚糖蕴藏量仅次于纤维素,是极其丰富的可再生资源。以壳聚糖为壁材凝聚法制备胶囊过程比较简单,成囊机理明确,制备周期短,全程150min左右。整个过程以水为介质,没有高温高压催化过程,对人和环境无危害、无污染。壳聚糖超细胶囊的开发与应用具有广阔的前景。更多还原

【Abstract】 In this paper, we put forward the concept of ultrafine capsules, expatiated on the preparation methods, application fields and technology progress, reviewed the structure and function of chitosan, and analyzed the feasibility and preparation significance of capsule from chitosan. According to these, we put forward the research scheme of the ultrafine capsules preparation from chitosan as wall and vitamin E, solution of crystal violet lactone （CVL）, nano-TiO₂ as core by monophasic coagulation and complex coagulation process. We studied the technological process conditions, such as emulsifying conditions, fixing conditions, wall-material concentration, wall-material ratio, the ratio of core to wall, drying temperature, and determined the optimum process parameters. The capsule performance and capsule formation mechanism were characterized, tested and analyzed by some apparatus and means such as laser particle sizer, SEM （Scanning Electron Microscope）, FTIR （Fourier Transformation Infrared Spectrum） and HPLC （High Performance Liquid Chromatogram）.Ultrafine capsules were prepared by monophasic coagulation process using chitosan as wall material and V_e as core material. The deacetylation degree of chitosan should be more than 85%, molecular weight of chitosan about 9× 10⁵, solution concentration 1.0%, core/wall ratio 1:1, emulsifier dose 6.0%, emulsifying stirring rate 9 000-10 000r/min. Through the characterization, test and analysis of capsule performance, we knew the capsule particle size is less than 3μm, the particle uniformity is good, the shape is basically sphericity, the embedding ratio of core material V_e is 86.1%, the heat endurance and stability of capsule is good. The product performance has reached the overseas advanced level.Ultrafine capsules were prepared by complex coagulation process using chitosan- sodium alginate as wall material and CVL as core material. The wall material ratio is 1:1, wall material concentration 1.0%, emulsifier dose 6.0%, emulsifying time 30min, hardener dose 10ml, hardening time 1h. Through the characterization, test and analysis of capsule performance, we knew the capsule particle size is less than 3μm, the particle uniformity is good, and the embedding ratio of core material is 82.6%. The heat endurance, stability and core material embedding ratio of capsule have reached the highest level compared with the capsules prepared from natural materials by complex coagulation process.Ultrafine capsules were prepared by monophasic coagulation process using chitosan as wall material and nano-TiO₂ as core material. The optimum core/wall ratio 1:1 1.6:1. Nano-TiO₂ can be dispersed in wall material solution by ultrasonic. The dispersion results are good. This is propitious to the chitosan embedding or the absorption in the capsule surface. Through the characterization, test and analysis of capsule performance, we knew the capsule particle size is less than 2μm, the particle uniformity is good, and the capsule has very good dispersion in organic phase. The Ultraviolet ray absorption of capsules is higher than that of nano-TiO₂. The Ultraviolet-visible light reflectivity of capsules corresponds with that of nano-TiO₂. Theultrafine capsule was used in cosmetics.The experiment confirmed that the sense and physical and chemical index of cosmetics reached the national standard when adding the chitosan -Ve ultrafine capsules and the chitosan -nano-TiC>2 ultrafine capsules in cosmetics. Though test and analysis, the Ve content of cosmetics reduced 8.7% after adding chitosan -Ve ultrafine capsules in cosmetics 15 days and the Ve content of cosmetics reduced 22.3% after adding Ve in cosmetics directly 15 days. This result showed that chitosan -Ve ultrafine capsules have the effect of protection and insulation Ve. The chitosan -nano-TiC?2 ultrafine capsules have very good dispersion in cosmetics and no flocculation after adding chitosan -nano-TiC>2 ultrafine capsules in cosmetics. The chitosan -nano-TiC>2 ultrafine capsules have very good solubility in organic phase. The Ultraviolet-visible light reflectivity of cosmetics with chitosan -nano-TiC>2 ultrafine capsules is no obvious difference from that with nano-TiC>2. CB paper of carbonless copy paper prepared with chitosan-sodium alginate-CVL ultrafine capsules. All the properties reached the domestic advanced level of congeneric products.The reserves of chitosan is only inferior to cellulose. Chitosan is a very abundant regenerable resource. The preparing process of capsules by monophasic coagulation process using chitosan as wall material is relatively simple. The formation mechanism of capsules is clear. The period of the preparing process is short, and the whole period is about 150 min. Water is medium in the whole process, without high temperature and high pressure. It is friendly with human and environment. Therefore, the development and application of chitosan ultrafine capsules have very broad foreground.更多还原