【作者】 丁兆云；

【导师】 郝爱友；

【作者基本信息】 山东大学 ， 有机化学， 2007， 博士

【摘要】 探索并研究高性能的新型表面活性剂一直是人们感兴趣的课题。Gemini表面活性剂是一类新型的表面活性剂，它是用联接基团将两个普通表面活性剂分子的亲水头基或在靠近头基处以化学键方式联接在一起形成的。与普通表面活性剂相比，该类表面活性剂表面性能优异，具有独特的聚集体形态和流变性，且与普通表面活性剂的协同作用更好。本论文设计、合成了两类新型Gemini阳离子表面活性剂、一类新型Gemini两性离子型表面活性剂、一类双长链烷基聚氧乙烯型非离子表面活性剂和一类双长链季铵盐型表面活性剂，用IR、¹H NMR、MS和元素分析等分析手段表征了其化学结构，探讨了它们的表面性能以及泡沫性能，并与其相应的单体表面活性剂和结构相近的Gemini表面活性剂进行了比较，还探讨了双长链烷基聚氧乙烯型非离子表面活性剂对辛伐他汀的增溶、具有特殊疏水链的新型Gemini阳离子表面活性剂对萘、1-萘酚和2-萘酚的增溶以及聚甘油酯在微乳化汽油中的应用。另外，运用DSC、POM和XRD三种表征方法，确定了双长链季铵盐和Gemini两性离子型液晶化合物的液晶类型。论文包括以下研究内容：1．具有特殊疏水链的新型Gemini阳离子表面活性剂——设计、合成与性能为了得到结构新颖、性能优异的Gemini阳离子型表面活性剂，本文以长链脂肪醇（十二醇、十四醇、十六醇）、环氧氯丙烷、二甲胺和1，4-二溴丁烷为原料，设计、合成了3个在疏水链靠近头基处引入羟基的新型Gemini阳离子表面活性剂{[C₁₂H₂₅-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₂]₂，2Br^-，简称3a、[C₁₄H₂₉-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₂]₂，2Br^-，简称3b和[C₁₆H₃₃-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₂]₂，2Br^-，简称3c}：用IR、¹H NMR、MS和元素分析表征其结构；通过表面张力法研究其表面性能，如临界胶束浓度（CMC）、平衡表面张力(γ_CMC)、表面最大吸附量(Γ_CMC)、分子最小截面积(A_CMC)、降低表面张力的效率(pC₂₀)、表面活性剂在界面的吸附能力与在体相形成胶束能力的相对强弱之比(CMC／pC₂₀)以及泡沫性能等，并与相应的单体表面活性剂和结构相近的Gemini阳离子表面活性剂{[C₁₂H₂₅N⁺（CH₃）₂-（CH₂）₂]₂，2Br^-，即C₁₂-4-C₁₂}进行了比较，从而探讨在疏水链靠近头基处引入羟基对Gemini阳离子型表面活性剂表面性能的影响，进一步揭示表面活性剂的结构与性能之间的关系。对比研究结果表明，3a的CMC比C₁₂-4-C₁₂的低5倍，且3a的γ_CMC也比C₁₂-4-C₁₂的低1.4dyne／cm。显然，在疏水链靠近头基的地方引入羟基，提高了Gemini阳离子型表面活性剂的表面性能。原因可能是羟基之间形成了分子内或者分子间氢键，促进了疏水链间的疏水作用力，从而提高了表面活性剂的性能。该类新型Gemini阳离子表面活性剂的CMC值随疏水链的增长而逐渐较小，说明形成胶束的能力逐渐增强；并且它们的CMC比相应的单体表面活性剂的小1个多数量级，表明Gemini表面活性剂形成胶束的能力更强。γ_CMC随疏水链的增长而逐渐增大。pC₂₀随疏水链的增长而逐渐增大、且较大，表明该类表面活性剂具有良好的降低表面张力的效率。3a的CMC／pC₂₀为3.97，较大，说明3a更倾向于吸附在气液界面上；由于多层吸附，3b的CMC／pC₂₀较小。另外，该类新型Gemini阳离子表面活性剂3a和3b具有良好的泡沫性能。本文还以临界胶束浓度的倍数为单位探讨了3a、3b和3c对萘、1-萘酚和2-萘酚的增溶能力。研究发现：3a、3b和3c对极性有机污染物1-萘酚和2-萘酚的增溶能力明显强于对萘的增溶能力，可能是因为它们在胶束中的增溶位置不同。在相同临界胶束浓度倍数的情况下，这3个新型Gemini阳离子表面活性剂对萘、1-萘酚和2-萘酚增溶能力的顺序为3a＞3b＞3c。此项研究成果将为该类表面活性剂在环境治理方面的应用提供理论指导。综上所述，当分子结构设计合理时，可以得到表面性能优异且具有良好泡沫性能的Gemini阳离子型表面活性剂。2．具有特殊联接基团的新型Gemini阳离子型表面活性剂——设计、合成与性质为了获得表面性能优异、结构新颖的Gemini阳离子型表面活性剂，本文以对苯二酚、环氧氯丙烷为起始原料合成了中间体对苯二酚二缩水甘油醚；此中间体与长链烷基二甲基叔胺及其盐酸盐反应合成了3个新型Gemini阳离子型表面活性剂[C₁₂H₂₅-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₂H₂₅，2Cl^-，简称A、C₁₄H₂₉-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₄H₂₉，2Cl^-，简称B和C₁₆H₃₃-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₄H₂₉，2Cl^-，简称C]，该类Gemini表面活性剂的联接基团既含有刚性疏水苯环，苯环两侧又有柔性亲水基团2-羟基-1，3-亚丙基。用IR、¹H NMR、MS和元素分析表征其化学结构进，采用表面张力法探讨了它们的表面性能(如CMC值、γ_CMC、Γ_CMC、A_CMC、pC₂₀和CMC／pC₂₀)，还测定了其泡沫性能，并与相应的普通表面活性剂E[C₁₂H₂₅-N⁺（CH₃）₃，Cl^-]和结构相近的Gemini阳离子表面活性剂D[C₁₂H₂₅-N⁺（CH₃）₂-CH₂-C₆H₄-CH₂-N⁺（CH₃）₂-C₁₂H₂₅，2Cl^-]进行了比较，从而探讨在刚性联接基团苯环的两侧引入柔性、亲水联接基团对Gemini表面活性剂性能的影响，进一步揭示表面活性剂的结构与性能的关系。对比研究结果表明，A的CMC比D的小了3.6倍，而且A的γ_CMC比D的小1.8dyne／cm。这说明：在刚性联接基团苯环的两侧引入柔性、亲水联接基团2-羟基-1，3-亚丙基提高了Gemini阳离子表面活性剂表面性能。可能是由于柔性联接基团的引入降低了苯环的刚性，增强了疏水链间的疏水作用力，从而提高了表面活性剂的表面性能。此外，A的CMC比E的小1个多数量级。随疏水链的增长，该类Gemini季铵盐型阳离子表面活性剂的CMC值和A_CMC逐渐较小、pC₂₀和Γ_CMC逐渐增大，说明随疏水链的增长，表面活性剂形成胶束的能力以及降低表面张力的效率逐渐增强。LogCMC与疏水链上碳原子数m之间呈线性下降关系。另外，γ_CMC随疏水链的增长逐渐增大。A的CMC／pC₂₀较大，说明A更倾向于吸附在气液界面上；由于多层吸附，B的CMC／pC₂₀较小。随疏水链的增长，该类新型Gemini阳离子表面活性剂的发泡能力逐渐降低、泡沫稳定性逐渐升高。与E相比，A和B具有良好泡沫性能。研究结果表明：当分子结构设计合理时，可以得到表面性能优异且具有良好泡沫性能的Gemini阳离子型表面活性剂。3．聚甘油酯的合成及其对汽油微乳化的研究能源危机的加剧及人们对环保的日益重视使微乳化燃油的研究成为热点课题。聚甘油酯是基于天然再生资源的、且广泛应用的非离子型表面活性剂。本文将聚甘油酯应用于微乳化汽油的研究，目的在于拓宽其应用领域。本文中首先合成了四个聚甘油酯[三聚甘油二异硬脂酸酯（TGDIS）、五聚甘油二硬脂酸酯（PGDS）、三聚甘油单硬脂酸酯（TGMS）和三聚甘油争油酸酯（TGMO）]，研究了它们与油酸钠以及助表面活性剂（正丁醇、异丁醇、正丙醇和异丙醇）在形成微乳化汽油时的协同作用。实验结果表明：在所考察的四个聚甘油酯中，TGDIS与油酸钠的协同增溶水的性能最好；正丁醇为最佳助表面活性剂；TGDIS／油酸钠的最佳质量比为6∶4。在最佳条件及16℃时，当表面活性剂的总量和汽油的量分别为0.740和6.000g时，TGDIS／油酸钠／正丁醇／汽油／水微乳体系的最大增溶水量为2.402g。本文中还考察了形成微乳化汽油时AEO₉与TGDIS的协同作用，并同TGDIS／油酸钠作了对比。当TGDIS／油酸钠、TGDIS／AEO₉的质量比为6∶4时（最佳质量比），TGDIS／油酸钠／正丁醇／汽油／水微乳体系比TGDIS／AEO₉／汽油／水微乳体系增溶更多的水，且对温度的敏感性更差，这是由于阴离子表面活性剂油酸钠对温度不像非离子表面活性剂AEO₉那样敏感。因此，TGDIS／油酸钠／正丁醇／汽油／水微乳体系更理想。本文的研究成果为聚甘油酯在微乳化汽油中应用提供了理论重要依据，也有助于我们理解乳化剂的结构与性能之间的关系。4．聚氧乙烯三聚甘油二异硬脂酸酯的合成、性能及其对药物的增溶三聚甘油二异硬脂酸酯（PGDIS）是带有两个长疏水链的亲油性非离子表面活性剂，在室温下为液态，以它为原料合成了3个具有不同乙氧基数的聚氧乙烯三聚甘油二异硬脂酸酯亲水性非离子表面活性剂PGDIS-E36、PGDIS-E40和PGDIS-E58，用¹H NMR确定了其乙氧基的数目（EO数），探讨了它们的物理性能、表面性能、乳化性能、泡沫性能、相对粘度及对新伐他汀的增溶性能，并同Tween-80进行了比较。Tween-80是一种广泛应用的非离子表面活性剂，它的疏水链上含有不稳定的碳碳双键，这限制了其应用。通过本文的研究，期望寻找到在某些应用方面能够替代Tween-80的产品。在室温下，PGDIS-E36和PGDIS-E40呈液态，PGDIS-E58为膏状，它们的水溶性都非常好，且浊点都大于100℃。由于盐析效应，硫酸钠降低了该类非离子型表面活性剂的浊点。因为PGDIS-E36、PGDIS-E40和Tween-80 HLB值相近，硫酸钠对这些表面活性剂浊点的影响极为相似；另外，当硫酸钠的浓度大于4.5％，它对具有较长EO链的PGDIS-E58浊点的影响更大。PGDIS-E36、PGDIS-E40和PGDIS-E58的临界胶束浓度都小于0.01mmol l^-1，比Tween-80的小1个数量级之多；而且PGDIS-E36、PGDIS-E40和PGDIS-E58的乳化能力都比Tween-80强。聚氧乙烯三聚甘油二异硬脂酸酯乳化能力的顺序为PGDIS-E58＞PGDIS-E40＞PGDIS-E36。此外，PGDIS-E36和PGDIS-E40与Tween-80的泡沫性能相近，相对粘度也相当。PGDIS-E36、PGDIS-E40和PGDIS-E58对辛伐他汀的增溶能力大于Tween-80，且具有适中HLB值的PGDIS-E40对辛伐他汀的增溶能力最强。PGDIS-E40与乙醇复配使用更有利于辛伐他汀的增溶，适当提高增溶体系温度、适量增加氯化钠含量都能提高PGDIS-E40对辛伐他汀的增溶能力。聚氧乙烯三聚甘油二异硬脂酸酯与Tween-80的分子结构不同，前者的分子中有两个疏水链，这增强了表面活性剂分子的疏水作用力，表现出更好的表面性能、乳化性能、增溶性能。因此，聚氧乙烯三聚甘油二异硬脂酸酯有望在某些应用方面替代Tween-80。5．双长链季铵盐液晶化合物的设计、合成与表征以长链脂肪醇和环氧氯丙烷为原料制备了中间体长链烷基缩水甘油醚，此中间体再与长链烷基二甲基叔胺及其盐酸盐反应合成了9个对称和不对称双长链季铵盐液晶化合物{[R₁-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R₂，Cl^-]，R₁，R₂：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃}，用¹H NMR、MS和元素分析表征了它们的化学结构，用DSC、POM和XRD三种表征方法，探讨了双长链季铵盐液晶化合物的液晶行为，以及碳氢链长度、分子对称性对该类液晶化合物的液晶行为的影响。研究结果表明：以上两个因素只影响了该类液晶化合物的熔点、清亮点和液晶区间，但并未改变其液晶类型。随碳氢链长度的增长和分子不对称性程度的增强，液晶化合物的熔点和清亮点逐渐降低、液晶相温度范围变窄。在液晶相温度范围内，它们都出现了丝状、网状、十字轮、扇形和纹影织构，并且它们在小角处有极弱的衍射峰，在广角处（2θ≈20°）有宽弥散峰。由此可以判定这9个双长链季铵盐化合物均属于胆甾型液晶。6．Gemini两性离子型液晶化合物的设计、合成与表征以长链脂肪醇、环氧氯丙烷、长链烷基二甲基叔胺及其盐酸盐和氯磺酸合成了3个双长链季铵盐{[R-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R，Cl^-]，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃}和3个Gemini两性离子型液晶化合物[R-O-CH₂-CH（OSO₃^-）-CH₂-N⁺（CH₃）₂-R，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃]，用IR、¹H NMR、MS和元素分析表征了它们的结构，用DSC、POM和XRD三种表征方法，对比研究了这两类液晶化合物的液晶行为。研究结果表明：双长链季铵盐液晶化合物的熔点和清亮点较低、液晶相温度范围较窄；Gemini两性离子型液晶化合物具有更高的熔点和清亮点、更宽的液晶相温度范围及更好的热稳定性；双长链季铵盐液晶化合物属于胆甾型液晶，Gemini两性离子型化合物第一个相区为晶体间晶型之间的转变，第二个相区为近晶相Sc。由此可见，碳氢链的长度能够影响液晶化合物的熔点、清亮点和液晶相区间的大小，化合物的类型能够显著改变液晶化合物的以上液晶性质和热稳定性，化合物的类型不同液晶类型也不同。7．论文的创新点（1）首次设计、合成了3个在疏水链靠近头基处引入羟基的新型Gemini阳离子型表面活性剂{[R-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-R，2Br^-]，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃}，用IR、¹H NMR、MS和元素分析等分析手段对它们的结构进行了表征，探讨了它们的表面性能、泡沫性能以及对有机物污染物的增溶性能。研究结果表明：在疏水链靠近头基的地方引入羟基，提高了Gemini阳离子型表面活性剂的表面性能。（2）首次设计、合成了3个新型Gemini阳离子型表面活性剂{[R-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R，2Cl^-]，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃}，用IR、¹H NMR、MS和元素分析等分析手段对它们的结构进行了表征，探讨了它们的表面性能、泡沫性能。研究结果表明：在刚性联接基团苯环的两侧引入柔性、亲水联接基团提高了Gemini阳离子型表面活性剂表面性能。（3）本文首次将聚甘油酯应用于微乳化汽油的研究。聚甘油酯（三聚甘油二异硬脂酸酯、五聚甘油二硬脂酸酯、三聚甘油单硬脂酸酯和三聚甘油单油酸酯）与油酸钠以及助表面活性剂（正丁醇、异丁醇、正丙醇和异丙醇）在形成微乳化汽油时有很好协同作用，其中三聚甘油二异硬脂酸酯最为理想，它与油酸钠和正丁醇在微乳化汽油中具有最佳的协同增溶水的性能。此研究成果为聚甘油酯在微乳化汽油中应用提供了重要依据。研究论文发表在Fuel 2007，86（4），597-602。（4）本文首次以带有两个长疏水链的亲油性非离子表面活性剂三聚甘油二异硬脂酸酯合成了3个聚氧乙烯三聚甘油二异硬脂酸酯亲水性非离子表面活性剂——PGDIS-E36、PGDIS-E40和PGDIS-E58，探讨了它们的物理性能、表面性能、乳化性能及对新伐他汀的增溶性能，并同Tween-80进行了比较，为PGDIS-E36、PGDIS-E40和PGDIS-E58在某些应用方面替代Tween-80提供了重要依据。研究论文发表在J．Disp．Sci．Tech．2007，28（4），495-500。（5）首次设计、合成了9个双长链季铵盐液晶化合物[R₁-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R₂，Cl^-，R₁，R₂：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃]，并用IR、¹H NMR、MS和元素分析等分析手段对它们的结构进行了表征，采用DSC、POM和XRD三种表征方法，确定了该类液晶化合物的液晶类型。（6）首次设计、合成了3个Gemini两性离子型液晶化合物[R-O-CH₂-CH（OSO₃^-）-CH₂-N⁺（CH₃）₂-R，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃]，并用IR、¹H NMR、MS和元素分析等分析手段对它们的结构进行了表征，采用DSC、POM和XRD三种表征方法，确定了[R-O-CH₂-CH（OSO₃^-）-CH₂-N⁺（CH₃）₂-R，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃]的液晶类型，并同[R-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R，Cl^-，R：C₁₂H₂₅，C₁₄H₂₉，C₁₆H₃₃]作了比较。更多还原

【Abstract】 It always attracts much interest to investigate new surfactants with high performances. Gemini surfactant is a new class of surfactants. The surfactant is made up of two amphiphilic surfactants-like moieties connected at the level of head group or very close to head group by a spacer of varied nature. In comparison to its corresponding conventional surfactant, Gemini surfactant shows better surface-active property, extremely interesting rheological property, unusual micelle structure and aberrant aggregation behavior, and better synergism with conventional surfactant. Two series of novel cationic Gemini surfactants, a new series of zwitterionic Gemini, a new class of nonionic surfactants with two long-chain alkyls and a new series of double-chain quaternary ammonium salts have been synthesized and characterized through IR, ¹H NMR, MS and elementary analysis. Their surface-active properties and foaming properties have been investigated in comparison with their corresponding single-chain surfactants and other cationic Gemini surfactants with similar chemical structures. Solubility of simvastatin in the micelles of the new synthesized nonionic surfactants （polyglycerol diisostearate ethoxylates）, solubility of naphthalene, 1-naphthol and 2-naphthol in the micelles of the new synthesized cationic Gemini surfactants {[R-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-R, 2Br^-], R: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃} with hydroxyl in hydrophobic chain nearby head group have also been researched. Water-in-gasoline microemulsions stabilized by polyglycerol esters have been examined. The thermal phase behaviors of the new synthesized double-chain quaternary ammonium salts and zwitterionic Geminis have been characterized by differential scanning calorimetry （DSC）, a polarized optical microscopy （POM） equipped with a heating stage and X-ray diffraction （XRD）.The detail investigations of the paper are as following:1. A series of novel cationic Gemini surfactants with special hydrophobic chains: design, synthesis and performancesIn order to obtain cationic Gemini surfactants with novel chemical structures and excellent properties, a series of novel cationic Gemini surfactants: 3a[C₁₂H₂₅-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₁₂H₂₅, 2Br^-] 、 3b [C₁₄H₂₉-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₁₄ H₂₉, 2Br^-] and 3c [C₁₆H₃₃-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₁₆H₃₃,2Br^-] with hydroxyl in hydrophobic chain nearby head group have been designed and synthesized using long chain alcohols （dodecanol, tetradecanol and hexadecanol）, epichlorohydrin, dimethylamine and 1,4-dibromo-butane. The chemical structures of the newly designed Gemini surfactants have been characterized by means of IR, ¹H NMR, MS and elementary analysis. Surface-active properties involving critical micellar concentration （CMC）, equilibrium surface tension of surfactant aqueous solution at concentration of CMC （γcmc） surface excess concentration at surface saturation (Γ_cmc), area per molecule at the air/water interface at surface saturation (A_cmc), negative logarithm of the bulk liquid phase concentration of surfactant required to depress surface tension of solvent by 20mM/m (pC₂₀), a measure of surfactant preference for adsorption relative to micellization (CMC/C₂₀ ratio), and foam properties of these cationic Gemini surfactants have been investigated, in comparison with their corresponding single-chain surfactants and other cationic Gemini surfactants{[C₁₂H₂₅-N⁺（CH₃）₂-（CH₂）₂]₂, 2Br^-, (C₁₂-4-C₁₂ } with similar structures of the synthesized surfactants. The purpose of this research is to investigate the effect of introducing hydroxyl in hydrophobic chain nearby head group on properties of surfactants, which can reveal the relationship between structure and property of Gemini surfactants.The obtained experimental results indicate that the CMC and γcmc value of the novel cationic Gemini surfactant （3a） are both lower than those of C₁₂-4-C₁₂ . This may be due to the formation of hydrogen bonds between hydroxyls inter molecules or inner molecules, which increases attraction between hydrophobic chains. Thus molecules of Gemini surfactant pack more tightly at the air/water interface. It is concluded that introducing hydroxyl in hydrophobic chain nearby head group can improve surface-active properties of the novel cationic Gemini surfactants.It has been found that the CMC of the synthesized cationic Gemini surfactantsdecreases with the increase of hydrophobic chain length, which indicates that the ability to form micelles in the bulk solution increases with the increase of hydrophobic chain length. Furthermore, the critical micelle concentrations of 3a 、 3b and 3c are all one order of magnitude lower than those of their monomeric surfactants. The results suggest that Gemini surfactants exhibit better surface-active properties. However the γ_CMC value increases with the increase of hydrophobic chain length.The PC₂₀ of the novel cationic Gemini surfactants increases with the increase of hydrophobic chain length. In addition, their PC₂₀ is larger, which indicates Gemini surfactants are more efficient in reducing surface tension of water. The CMC/C₂₀ ratio of 3a is 3.97, which is larger. This indicates that 3a shows greater tendency to adsorb at water/air interface. However, the CMC/C₂₀ ratio of 3b is relative small. This may be due to the formation of multilayers.Foaming ability decreases and foam stability increases with increasing hydrophobic chain length of the novel cationic Gemini surfactants. The 3a and 3b exhibit better foaming ability and foam stability.The solubilization of naphthalene, 1- naphthol and 2- naphthol in the micelles of the novel cationic Gemini surfactants have been examined as a function of surfactant concentration （multiple of CMC）. The solubilization power of the micelles for 1 -naphthol and 2- naphthol is much better than that for naphthalene. This result may be due to the different polarities of naphthalene, 1- naphthol and 2- naphthol, which lead to different positions solubilized of them. The solubilization power of the micelles of synthesized cationic surfactants is in order of 3a > 3b > 3c.The result of this research may provide proof for applications of the novel Gemini surfactants in environmental treatment.It can be drawn from the results of the capter that cationic Gemini surfactants with excellent surface-active properties and good foaming properties can be obtained through reasonable design and synthesis.2. A series of novel cationic Gemini surfactants with a special spacer group: design, synthesis and propertiesIn order to obtain cationic Gemini surfactants with novel chemical structures and excellent properties, a series of the novel cationic Gemini surfactants A [C₁₂H₂₅-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₂H₂₅,2Cl^-, ], B [C₁₄H₂₉-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₄H₂₉,2Cl^-], and C [C₁₆H₃₃-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C₆H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-C₁₆H₃₃, 2C1^-] having a spacer group with two flexible and hydrophilic spacer groups （2-hydroxyl-1, 3-propanediyl） in both sides of a rigid and hydrophobic spacer group （1,4-hydroquinonediyl） have been designed and synthesized by reaction of hydroquinone diglycidyl ether with long-chain tert-alkylamine and its hydrochloride. The chemical structures of the novel cationic Gemini surfactants have been characterized by IR, ¹H NMR, MS and elementary analysis. A comparative study involving surface-active properties (CMC, γcmc, Γ_cmc, Acmc, PC₂₀, CMC/C₂₀ ratio), and foaming properties of these cationic Gemini surfactants has been done for the novel cationic Gemini surfactants, their corresponding single-chained surfactants （E） [C₁₂H₂₅-N⁺（CH₃）₃, Cl^-] and other cationic Gemini surfactants （D） [C₁₂H₂₅-N⁺（CH₃）₂-CH₂-C₆H₄-CH₂-N⁺（CH₃）₂-C₁₂H₂₅, 2Cl^-]with similar structures of the newly designed Gemini surfactants. The purpose of this research is to investigate the effect of the structure of spacer group on properties of surfactants, which can reveal the relationship between structure and property of Gemini surfactants.It has been found that the CMC and γcmc value of the novel cationic Gemini surfactant （A） are both lower than those of the other cationic Gemini surfactant （D）, which indicates that the introduction of flexible and hydrophilic spacer groups in both sides of a rigid and hydrophobic spacer group can improve surface-active properties of cationic Gemini surfactants. Introducing flexible and hydrophilic spacer groups in both sides of a rigid and hydrophobic spacer group makes the spacer group less rigid, which increases the attraction between hydrophobic chains, and makes molecules of Gemini surfactant pack more tightly at the air/water interface.It has been also found that the CMC values decrease with increasinghydrophobic chain length of the novel cationic Gemini surfactants, which indicates that the ability to form micelles in the bulk solution increases with the increase of hydrophobic chain length. The CMC of the novel cationic Gemini surfactant （A） is one order of magnitude lower than that of the monomeric surfactant （E）. The results suggest that Gemini surfactants exhibit better surface-active properties. Furthermore, the logarithm of CMC decreases linearly with increasing the number of carbon atoms in the hydrophobic groups. However the γCMC value increases with the increase of hydrophobic chain length the novel cationic Gemini surfactants.The pC₂₀ of the novel cationic Gemini surfactants increases with the increase of hydrophobic chain length. In addition, their pC₂₀ is larger, which indicates Gemini surfactants are more efficient in reducing surface tension of water. The CMC/C₂₀ ratio of A is relative large. This indicates that A shows greater the tendency to adsorb at water/air interface. However, the CMC/C₂₀ ratio of B is relative small. This may be due to the formation of multilayers.In addition, foaming ability decreases and foam stability increases with increasing the hydrophobic chain lengths of the novel cationic Gemini surfactants. The A and B exhibit better foaming ability and foam stability than E.It can be concluded that cationic Gemini surfactants with excellent surface-active properties and good foaming properties can be achieved through reasonable designs and synthesis.3. Synthesis of polyglycerol esters and their applications in water-in-gasoline microemulsionThe research of microemulsion fuel has been increasingly attracting attentions, which may be due to the coming of energy emergency and great attention of human to environmental pollution. Polyglycerol esters of fatty acids （PGEFs）, which are widely used nonionic surfactants, are based on renewable raw materials. The purpose of the research is to widen the range of its application. Four polyglycerol esters of fatty acids including triglycerol diisostearate （TGDIS）, pentaglycerol distearate （PGDS）, triglycerol monostearate （TGMS） and triglycerol monooleate （TGMO） have been synthesized. The synergistic effects for the mixtures of PGEF （TGDIS, PGDS, TGMS or TGMO） with sodium oleate in solubilizing water in gasoline have been investigated. The effect of a series of alcohols （1-butanol, 2-butanol, 1-propanol and 2-propanol） on the water amounts solubilized in the microemulsion systems of TGDIS/sodium oleate/alcohol/ gasoline/water has been researched. It is shown that the microemulsion system of TGDIS/sodium oleate/1-butanol/gasoline/water exhibited better behavior in solubilizing water than the other systems studied. The best weight ratio of TGDIS/sodium oleate is 6:4, in which the maximum solubilization capacity of water is 2.402 g at 16°C, when the amount of the mixed surfactants and gasoline are 0.740 and 6.000g respectively.In addition, the microemulsion system of TGDIS/sodium oleate/1-butanol/ gasoline/water is more water soluble and less temperature sensitive, in comparison with the microemulsion system of TGDIS/lauryl polyoxyethylene （9） ether （AEO₉）/ gasoline/water at the best weight ratio of TGDIS/sodium oleate and TGDIS/ AEO₉ （6:4）. This may be due to less temperature sensitive of anionic surfactant （sodium oleate） than nonionic surfactant （AEO₉）. The result of this chapter provides potentially information for applications of polyglycerol esters in microemulsion gasoline. Moreover the results of the research can lead us to understand the relationship between the structure and the emulsifying ability of surfactants throughly. 4. Synthesis of triglycerol diisostearate ethoxylates, their surface properties and the solubilization of drugTriglycerol diisostearate is a hydrophobic nonionic surfactant with two long alkyl chains in its structure, which is a pale yellow liquid at room temperature. A series of triglycerol diisostearate ethoxylates （PGDIS-E36, PGDIS-E40 and PGDIS-E58） have been synthesized by the reaction of triglycerol diisostearate with ethylene oxide. Properties including water solubility, cloud point （CP）, CMC, emulsifying ability, foaming properties, relative viscosity, and solubilizing capacity of polyglycerol diisostearate ethoxylates for simvastatin have been investigated in comparison with those of Tween-80. Tween-80 is a nonionic surfactant widely used. There is an unsaturated bond in its structure, which is unstable in properties. So its practical application is limited in some ways. It is important to find a replacement of Tween-80 in some aspects.PGDIS-E36 and PGDIS-E40 are pale yellow liquid at room temperature; while PGDIS-E58 is a pale yellow paste-like solid. Polyglycerol diisostearate ethoxylates show excellent water solubility. The CP of these surfactants is all more than 100 °C. The effect of sodium sulfate on the CP of PGDIS-E36, PGDIS-E40 and Tween-80 is similar, which may be due to their similar HLB values. Furthermore, PGDIS-E58 with longer EO chain length is more sensitive to sodium sulfate, when the concentration of sodium sulfate is above 4.5%.The CMC values of polyglycerol diisostearate ethoxylates are less than 0.01mmol 1^-1, which is one order of magnitude lower than that of Tween-80. Furthermore, the emulsifying ability of polyglycerol diisostearate ethoxylates increases with an increase in the number of EO units, and it is also better than that of Tween-80. In addition, foaming properties, relative viscosity of PGDIS-E36, PGDIS-E40 and Tween-80 are similar.Polyglycerol diisostearate ethoxylates are all superior to Tween-80 in enhancing the solubility of simvastatin in their micelles. PGDIS-E40 with appropriate HLB value shows the best effect. The combined use of PGDIS-E40 with ethanol facilitates the solubility of simvastatin. The addition of salt or increasing temperature could result in enhancement of simvastatin solubility in the micelles of PGDIS-E40. The surface properties, emulsifying abilities and solubilization powers for simvastatin of polyglycerol diisostearate ethoxylates are superior to those of Tween-80, which may be due to their different chemical structures. There are two hydrophobic alkyl chains in the molecule of polyglycerol diisostearate ethoxylate. which can increase the attraction of molecules.The results of this chapter indicate that Tween-80 may be replaced by PGDIS-E36, PGDIS-E40 and PGDIS-E58 in some aspects.5. Design, synthesis and characterization of thermal phase behaviors of a series of double-chain quaternary ammonium saltsA series of symmetrical and asymmetrical quaternary ammonium salts with two long alkyl chains {[R₁-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R₂, Cl^-], R₁ R₂: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃} have been designed and synthesized by the reaction of the intermediates of long-chain 1-O-alkyl glycidyl ether including 1-O-dodecyl glycidyl ether, 1-O-tetradecyl glycidyl ether and 1-O-hexadecyl glycidyl ether with long-chained tert-alkylamine and its hydrochloride. Their chemical structures have been characterized through IR, ¹H NMR, MS and elementary analysis. Their thermal phase behaviors have been confirmed by DSC, POM and XRD.It has been found that the compound with longer alkyl chain length or being more asymmetric exhibits lower melting points （T_m）, isotropization temperature （T_i） and narrower mesophase temperature range. The results suggest that the chain length, symmetry and asymmetry affect T_m, T_i and mesophase temperature ranges, but has little influence on the class of thermal phase behaviors. In the temperature of mesophase range, these compounds show oily streaks, netlike, fan-shaped, schlieren texture. XRD results shows that there is a sharp reflex in the small angle region and a diffuse wide peak in the wide angle region. All these confirm that these compounds form cholesteric liquid crystal.6. Design, synthesis and characterization of thermal phase behaviors of a series of zwitterionic GeminisA series of novel zwitterionic Geminis [R-O-CH₂-CH（OSO₃^-）-CH₂-N⁺（CH₃）₂-R, R: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃] have been designed and synthesized by the reaction of double-chain quaternary ammonium salt with chlorosulfonic acid, then neutralized with sodium hydroxide. Their chemical structures have been characterized through IR. ¹H NMR, MS and elementary analysis. The thermal phase behaviors of zwitterionic Geminis have been examined by DSC, POM and XRD, in comparison with double-chain quaternary ammonium salts.It has been found that double-chain quaternary ammonium salts exhibit lower phase transition temperature and narrower mesophase temperature ranges, while zwitterionic Geminis exhibit higher phase transition temperature, wider mesophase temperature ranges, and better thermo-stability. The former forms Ch, while the latter forms Sc. Alkyl chain length, the class of amphiphilic compounds affect T_m, T_i and mesophase temperature ranges. Furthermore, the class of amphiphilic compounds can change the class of thermal phase behaviors, and change thermo-stability greatly. 7. The mail innovations of the paper（1） A series of novel cationic Gemini surfactants {[R-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-（CH₂）₄-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-R, 2Br^-], R: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃} with hydroxyl in hydrophobic chain nearby head group were first designed and synthesized. Their chemical structures have been characterized through IR, ¹H NMR, MS and elementary analysis. Surface-active properties, foam properties of these cationic Gemini surfactants have been investigated. The result of this research shows that introducing hydroxyl in hydrophobic chain nearby head group can improve surface-active properties.（2） A series of novel cationic Gemini surfactants {[R-N⁺（CH₃）₂-CH₂-CH（OH）-CH₂-O-C-6H₄-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）₂-R, 2C1^-], R: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃} having a spacer group with two flexible and hydrophilic spacer groups （2-hydroxyl-l, 3-propanediyl） in both sides of a rigid and hydrophobic spacer group （1, 4-hydroquinonediyl） and were first designed and synthesized. Their chemical structures have been characterized through IR, ¹H NMR, MS and elementary analysis. Surface-active properties, foam properties of these cationic Gemini surfactants have been investigated. The results of this research suggest that the introduction of flexible and hydrophilic spacer groups in both sides of a rigid and hydrophobic spacer group can improve surface-active properties of cationic Gemini surfactants.（3） Polyglycerol esters of fatty acids were first investigated in microemulsion gasoline. Polyglycerol esters of fatty acids including triglycerol diisostearate （TGDIS）, pentaglycerol distearate （PGDS）, triglycerol monostearate （TGMS） and triglycerol monooleate （TGMO） with sodium oleate and co-surfactants including 1-butanol, 2-butanol, 1-propanol and 2-propanol have good symergism in solubilizing water in microemulsion gasoline. In the four polyglycerol esters, TGDIS is the best one. The results of this research show that polyglycerol esters have potential value in microemulsion gasoline. The research paper has been published on Fuel 2007, 86（4）, 597-602.（4） A series of triglycerol diisostearate ethoxylates （PGDIS-E36, PGDIS-E40 and PGDIS-E58） were first synthesized using triglycerol diisostearate being hydrophobic nonionic surfactant Surface-active properties, emulsifying ability, foaming properties, relative viscosity, and solubilizing capacity of polyglycerol diisostearate ethoxylates for simvastatin have been investigated in comparison with those of Tween-80. This research provides important information for replacing Tween-80 by PGDIS-E36, PGDIS-E40 and PGDIS-E58 in practical applications. The research paper has been published on J.Disp. Sci. Tech. 2007,28（4）, 495-500.（5） A series of double-chain quaternary ammonium salts {[R₁-O-CH₂-CH（OH）-CH₂-N⁺（CH₃）-2-R₂, Cl^-], R₁, R₂: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃} were first designed and synthesized. Their chemical structures have been characterized by means of IR, ¹H NMR, MS and elementary analysis. Their thermal phase behaviors have been confirmed by DSC, POM and XRD.（6） A series of novel zwitterionic Geminis [R-O-CH₂-CH（OSO₃^-）-CH₂-N⁺ （CH₃）₂-R, R: C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃] were first designed and synthesized. Their chemical structures have been characterized using IR, ¹H NMR, MS and elementary analysis. The thermal phase behaviors of double-chain quaternary ammonium salts and zwitterionic Geminis have been confirmed by DSC, POM and XRD in comparison.更多还原