糖基表面活性剂蔗糖酷的研究.doc

糖基表面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
2004年}i月
女连理工大学博士学位论文题目名称
糖基表面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
摘要
摘要
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、反应温度、催化剂量、皂量、反应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，在此基础上，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佳合成方法。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对反应过程中体系单醋、二醋和多醋的变化进
行了跟踪研究，对反应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扫描仪对蔗糖酷反应过程中及产品中的脂肪酸醋、脂肪酸和脂肪酸皂、蔗
糖酷成分进行了分离及定量分析。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
糖等成分进行了分离。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表面张
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表面活性
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天然表面活性剂的研究与开发·........................................................1
1.1.1天然表面活性剂的含义与分类·.....................................................1
1.1.2糖基天然表面活性剂········································……’·‘二‘..............2
1.1.3糖基的功能···································································……’二‘}3
1.2蔗糖醋表面活性剂的研究与发展·...:..............................................3
1.2.1蔗糖酷的发展简史········································一“......................3
1.2.2蔗糖酷的合成·······································。··············……’二‘二”.......4
1.2.2.1酞氯酷化法·············4···································……‘·…”二“’‘’‘”}..4
1.2.2.2酉旨交换法·.............................................................................4
1.2.2.3酶催化合成·..........................................................................8
1.2.3蔗糖酷的精制·.......................................................................12
1.2.4蔗糖酷的分析·.......................................................................1.4
1.2.5蔗糖酷的物理化学性质·...........................................................15
1.2.5.1表面和界面化学性质·...........................................................15
1.2.5.2胶团的结构和性质·..............................................................16
1.2.5.3相行为·.............................................................................16
1.2.5.4蔗糖酷微乳液·······························································……16
1.2.5.5蔗糖醋囊泡·······························································……“·17
1.2.5.6流变行为·..........................................................................18
1.2.5.7发泡力和泡沫稳定性·...........................................................18
1.2.5.8乳化性能·..........................................··· .............................18
1.2.6蔗糖醋表面活性剂的应用·.................:......................................19
1.3活性蔗糖酷的开发·············。·····························……‘··…‘·’·’二‘’.“’·20
1.3.1活性蔗糖酷的发展简史·...........................................................20
1.3.2植物产生的蔗糖醋的提取和结构表征·.........................................21
1.3.3活性蔗糖酷的杀虫活性·...........................................................22
1.3.4活性蔗糖酷的合成·······························。·······，····················……23
1.3.5活性蔗糖酷的特点及其研究的意义·............................................24
1.4选题的背景和依据···················································……’二’........24
1.4.1蔗糖酷表面活性剂的合成、分析和构性关系研究·.............................24
大连理工大学博士学位论文
参考文献·......................................................................................25
第二章硬脂酸蔗糖酷的合成·.....................................................32
2.1引言·......................................................................................32
2.2实验········································································...............32
2.2.1试剂和仪器·..........................................................................32
2.2.2合成与分析·..........................................................................32
2.2.2.1硬脂酸蔗糖醋的甲醇法合成·..................................................32
2.2.2.2硬脂酸蔗糖酷的低皂无溶剂合成·............................................33
2.2.2.3硬脂酸蔗糖酷的中皂无溶剂合成·...............................................33
2.2.2.4反应物中硬脂酸甲酷含量的测定·............................................33
2.2.2.5产品的精制工艺·.................................................................33
2.2.2.6灰分的测定·.......................................................................33
2.2.2.7微乳粒径的测定·.................................................................33
2.3结果与讨论·.............................................................................33
2.3.1硬脂酸蔗糖醋甲醇法合成影响因素的研究。...................................33
2.3.1.1正交实验因素选择·..............................................................33
2.3.2硬脂酸蔗糖醋低皂无溶剂法合成的影响因素研究·..........................36
2.3.2.1皂的用量、反应时间对硬脂酸甲酷转化率的影响·..........................36
2.3.2.2催化剂和反应时间对硬脂酸甲醋转化率的影响·..........................37
2.3.2.3反应温度和反应时间对硬脂酸甲酷转化率的影响·.......................37
2.3.2.4酉旨糖比、反应时间与硬脂酸甲酷转化率的关系·.............................38
2.3.2.5不同单酷含量的蔗糖酷的合成·...............................................39
2.3.3硬脂酸蔗糖酷中皂无溶剂微乳合成的影响因素研究·.......................39
2.3.3.1高单酷含量蔗糖醋的合成···...................................................39
2.3.3.1.1皂的用量对脂肪酸醋转化率的影响·...................................... 39
2.3.3.1.2催化剂用量和反应时间对脂肪酸酷转化率的影响·....................40
2.3.3.1.3反应温度对脂肪酸酷转化率的影响·.........................................41
2.3.3.1.4酉旨糖比对脂肪酸酷转化率的影响·............................................42
2.3.3.1.5反应条件对粗产品中单酷含量的影响·......................................42
2.3.3.2低单酷含量蔗糖酷的合成·.....................................................43
2.3.3.2.1催化剂用量的影响·..............................................................43
2.3.3.2.2皂用量的影响·....................................................................44
2.3.3.2.3温度的影响··························································……’二‘二‘" 44
2.3.3.2.4酉旨糖比的影响·....................................................................45
目次
2.3.3.3反应过程中各糖酷成分的变化·...............................................45
2.3.4蔗糖酷的精制工艺研究·...........................................................47
2.3.5硬脂酸蔗糖醋产品的灰分·........................................................ 48
2.3.6硬脂酸蔗糖酷成本估算·........................................................... 49
2.4结论·......................................................................................49
参考文献·......................................................................................50
第三章硬脂酸蔗糖酷的组成和结构分析·...................................51
3.1引言·.......................................................，’ .............................51
3.2实验·......................................................................................51
3.2.1硬脂酸蔗糖醋产物的薄层色谱分析方法及条件·.............................51
3.2.2柱色谱分离·..........................................................................5 `
3.2.3 HPLC分析方法及条件··························································一52
3.2.4蔗糖酷的HPLC-MS分析方法及条件·............................................52
3.2.5蔗糖酷的ES工一MS分析方法及条件·...............................................53
3.2.6蔗糖酷的核磁共振分析方法及条件·............................................53
3.3结果与讨论·.............................................................................53
3.3.1硬脂酸蔗糖醋产品的TLC分析·..................................................53
3.3.1.1产品中蔗糖醋和残糖的分析·..................................................53
3.3.1.2产品中硬脂酸酸醋的分析·.................................................. 5 5
3.3.1.3产品中脂肪酸和皂的分析·.....................................................55
3.3.2蔗糖醋的柱色谱分离·..............................................................57
3.3.3蔗糖醋的HPLC分析·················································............... 1-57
3.3.4电喷雾电离质谱(ESI-MS)分析·..................................................60
3.3.5蔗糖醋的HPLC-MS分析·........................................................65
3.3.6蔗糖醋的核磁共振波谱分析·.....................................................69
3.4结论·......................................................................................7Q
参考文献·......................................................................................11
第四章棕搁酸、月桂酸和油酸蔗糖酷的合成及分析·.............................72
4.1弓!言··································，··············································……72
4.2实验·......................................................................................72
4.2.1试剂与仪器·........................................................................../2
4.2.2合成与分析·........................................................................../2
4.6结果与讨论·............................................................................./4
4.3.1棕搁酸蔗糖醋的合成与分析·.....................................................74
大连理工大学博士学位论文
4.3.1.1棕搁酸蔗糖酷的合成·..............................................................74
4.3.1.1.1酷糖比对粗蔗糖酷中单酷含量的影响·......................................74
4.3.1.1.2酉旨糖比对棕搁酸酷转化率的影·.. ... ... ... ... ... ... ... ... ... ... ... 7 5
4.3.1.2棕搁酸蔗糖酷的精制及灰分测定·...............................................75
4.3.1.3棕搁酸蔗糖醋的分析·.............................................................. 76
4.3.1.3.1薄层色谱(TLC)分析··············。·····················.....................76
4.3.1.3.2电喷雾质谱(ESI-MS )分析·..................................................77
4.3.1.3.3 HPLC-ELSD分析·········...·············································…...80
4.3.1.3.4棕搁酸蔗糖醋的HPLC-MS分析······························..................81
4.3.2月桂酸蔗糖醋的合成与分析·.....................................................84
4.3.2.1月桂酸蔗糖酷的合成·...........................................................84
4.3.2.1.1酉旨糖比对反应的影响·...........................................................84
4.3.2.2月桂酸蔗糖醋的精制·...........................................................84
4.3.2.3月桂酸蔗糖醋的分析·..............................................................85
4.3.2.3.1 TLC分析·····································································…...85
4.3.2.3.2电喷雾电离质谱(ESI-MS)分析·............................................86
4.3.2.3.3 HPLC-ESLD分析················，···························。············…...87
4.3结论····...................................................................................88
参考文献·......................................................................................89
第五章蔗糖醋的物化性质及应用研究·......................................90
5.1引言·......................................................................................90
5.2实验·················································································…}..90
5.2.2测试方法········································································……%
5.3结果与讨论·.............................................................................91
5.3.1表面和界面性质·....................................................................91
5.3.1.1表面张力和临界聚集浓度·.....................................................91
5.3.1.2界面性质·····································。··································……%
5.3.2硬水稳定性·..........................................................................104
5.3.3发泡力和泡沫稳定性·............................................................... 107
5.3.3.1蔗糖酷的发泡力·.................................................................104
5.3.3.2蔗糖酷的泡沫稳定性·...........................................................110
5.3.3.3蔗糖酷与其它表面活性剂复配的泡沫性质·................................113
5.3.4乳化性能·.............