2023年糖基表面活性剂蔗糖酷的研究.doc

糖基外表活性剂蔗糖酷的研究 李延科· 学科、专业: 指导教师: 论文完成时l可 应用化学 杨锦宗院士 张淑芬教授 2023年}i月 女连理工大学博士学位论文题目名称 糖基外表活性剂蔗糖酷的研究 学位论文130页 表格42个 插图89幅 学位论文完成日期: 评阅人: 指导教师:杨锦宗院士 教研室主任: 院(系)主任: Investigation on Sugar Based Surfactant: Sucrose Esters Li Yanke A Dissertattion Submitted to Dalian Univers妙of Technology for Doctor Degree ofApplied Chemistry Supervised by Processor Yang Jinzong and Professor Zhang Shufen April 18, 2 004 在碱性催化剂存在下，以蔗糖、硬脂酸酷(AS)为原料，采用甲醇法、低皂 无溶剂法及中皂无溶剂微乳法合成了一系列单醋含量不同的硬脂酸蔗糖酷。考 察了醋糖比、反响温度、催化剂量、皂量、反响残压等因素对硬脂酸酷转化率、 蔗糖醋产率及产品中单酷、二酷和多酷组成的影响，在此根底上，对三种合成 方法的优劣进行评估，并最终确定中皂无溶剂微乳合成法为最正确合成方法。用 该无溶剂微乳法还合成了不同单醋含量的棕搁酸蔗糖酷、月桂酸蔗糖酷和油酸 蔗糖醋。此外，用‘HPLC-ELSD对反响过程中体系单醋、二醋和多醋的变化进 行了跟踪研究，对反响过程中各糖酷成分的变化原因进行了初步的探讨。 采用TLC, HPLC-ELSD, ESI-MS, HPLC-MS等技术对硬脂酸蔗糖酷、棕 搁酸蔗糖酷及月桂酸蔗糖酷的组成进行了定性和定量分析。用不同的展开剂及 TLC扫描仪对蔗糖酷反响过程中及产品中的脂肪酸醋、脂肪酸和脂肪酸皂、蔗 糖酷成分进行了别离及定量分析。采用高效液相色谱及蒸发光散射检测器对硬 脂酸蔗糖酷、棕搁酸蔗糖酷及月桂酸蔗糖酷产品中的蔗糖单酷、二酷、多酷及 糖等成分进行了别离。以纯棕搁酸蔗糖醋的液相色谱峰作基准，对硬脂酸蔗糖 酷和棕搁酸蔗糖醋产品中的棕桐酸单酷、二醋和多酷以及硬脂酸单醋、二酷和 多醋的峰进行了归属和定量分析。利用电喷雾质谱对所有硬脂酸蔗糖醋、棕搁 酸蔗糖醋及月桂酸蔗糖醋的组成进行了定性分析。利用HPLC-MS及EIC技术 对蔗糖酷产品进行了分析。 研究了硬脂酸蔗糖酷、月桂酸蔗糖Ma、棕搁酸蔗糖酷的结构组成与外表张 力、界面张力的关系。通过简化Hanson's三维模型，提出了两维溶解度参数模 型，根据不同蔗糖单醋、二酷和三酷在水和溶剂中的溶解性能及相应的溶解度 参数对它们进行了分区。根据每一种蔗糖酷所处的区及它所对应的相互作用半 径的不同，对蔗糖酷的界面现象进行了分析和解释。 研究了硬脂酸蔗糖酷、月桂酸蔗糖酷、棕搁酸蔗糖酷的结构组成与发泡力、 硬水稳定性、乳化力等性能的关系。研究了蔗糖醋与阴离子和非离子外表活性 剂的复配性能及不同单醋含量、不同脂肪酸链长及不同浓度的蔗糖酷对荔枝的 保鲜效果。 关键词:蔗糖酷，合成，精制，分析，性质，荔枝，涂层剂，两维溶解度参数 Abstract Abstract Sucrose stearates with the different proportion of monoesters were prepared by reacting sucrose and alkyl searate (AS) in the presence of alkali catalyst by "methanol process", "low soap solvent-free process" and“medium soap solvent-free microemulsion process". The influences of molar ratio of AS to sucrose reaction temperature, the amount of catalyst and soap, and residual pressure etc. on the conversion of AS, the yield of sucrose esters and the proportion of mono-, di- and polyesters were investigated. On the basis of comparison of superiority of these three processes, the medium soap solvent-free microemulsion process was opted as the final process for producing sucrose esters. Sucrose palmitates, sucrose laurates and sucrose oleates were also prepared form the solvent-free process. In addition, changes in the proportion of mono-, di- and polyesters in reaction process were monitored by HPLC-ELSD. Some analytical techniques, such as TLC, HPLC-ELSD, ESI-MS, HPLC-MS, were applied for the analysis of sucrose stearates, sucrose palmitates and sucrose laurates. The qualitative and quantitative results of the sucrose esters, soap, fatty acid, sucrose and fatty acid ester in crude and purified products were obtained by using TLC and TLC scanner and different separate agents. HPLC-ELSD was also used for the separation of sucrose monoesters, diesters and polyesters. Pure sucrose palmitates were prepared and used for the identification of mono-, di- and polypalmitates in sucrose stearates and sucrose palmitate. Commercial and synthesized sucrose esters containing mono-, di-, tri- or higher esters were qualitatively analyzed using electrospray ionization-mass spectrometry (ESI-MS). Sucrose esters were also analyzed by high-performance liquid chromatography (HPLC) in combination with electrospray ionization mass spectrometric detection in positive ion mode. Relationships of the composition and structure of sucrose esters to interfacial properties were investigated. A two-dimensional model of solubility parameters was established by simpli斤ing the Hansen's three-dimensional model. The model comprises three areas corresponding to solubility parameter and solubility of different sucrose esters. According to the interaction R, interfacial phenomena of different sucrose monoesters, diesters, triesters and some commercial sucrose esters and synthesized sucrose esters at oil-water interface can be interpreted logically. Some physiochemical properties of sucrose esters, such as foamability and form stability, stability in hard water and emulsifying power were investigated. The synergism of sucrose esters with other surfactants and effect of sucrose ester coating on storage life and quality of litchi was evaluated. KEY WORDS: Sucrose Esters, Synthesis, Purification, Ananlysis, Properties, Lithi, Coating agent, Two-Dimensional Model of Solubility 目次 目次 前言···················································。···································……l- 第一章文献综述·.......................................................................1 1.1天然外表活性剂的研究与开发·........................................................1 1.1.1天然外表活性剂的含义与分类·.....................................................1 1.1.2糖基天然外表活性剂········································……’·‘二‘..............2 1.1.3糖基的功能···································································……’二‘}3 1.2蔗糖醋外表活性剂的研究与开展·...:..............................................3 1.2.1蔗糖酷的开展简史·······················