【作者】 李奠础；

【导师】 王志忠； 李瑞丰；

【作者基本信息】 太原理工大学 ， 应用化学， 2007， 博士

【摘要】 表面活性剂是一类具有亲水基和憎水基的双亲结构的化合物。其分子可通过弱相互作用力自组装成具有多种重要功能的各种有序分子组合体。烷基二苯醚双磺酸钠（ADPODS）是一类当前备受瞩目的新型多功能双亲水基型阴离子表面活性剂。本研究以脂肪醇和二苯醚为原料,采用烷基化—磺化—中和的合成路线,合成了一系列烷基二苯醚双磺酸钠表面活性剂(C₈-MADS,C₉-MADS,C₁₆-MADS),并通过IR、XRD等物理化学表征手段研究了它们的表面活性及胶团聚集体系的性能。同时,研究了C₁₆-MADS与Gemini酯基季铵盐表面活性剂（Ⅱ-12-n,n=3,4,6）组成的二元复配体系(C₁₆-MADS/Ⅱ-12-n)、以及C₁₆-MADS与十二烷基二甲基羟乙基氯化铵（K₃）和脂肪醇聚氧乙烯醚（AEO₉）组成的三元复配体系(C₁₆-MADS/K₃/AEO₉)时的复配性能,并考察此类表面活性剂在水溶液中的界面张力性能及其对皮肤的安全性能。1、采用成本相对低廉的中碳醇(C₈、C₉、C₁₆)和二苯醚为原料,在浓硫酸催化下制备系列烷基二苯醚。然后采用发烟硫酸对其进行磺化,制备得到目标产物—系列烷基二苯醚双磺酸钠。通过对产物的表征分析,对其结构进行了鉴定,并对合成反应的影响因素进行了分析讨论,优化了合成条件。2、测定了所合成的系列烷基二苯醚双磺酸钠(C₈-MADS,C₉-MADS,C₁₆-MADS)的表面化学性能,结果表明:合成样品在质量分数高达10%的无机酸、无机碱及无机盐溶液中表面化学性能稳定,同时显示出优良的乳化性能和在硬水条件下较好的去污洗涤性能。3.复配体系具有降低表面张力效率的协同效应和形成胶团能力的协同效应。通过测定C₁₆-MADS与Ⅱ-12-n混合溶液的表面张力（γ）,并作γ～1gc曲线,对C₁₆-MADS/Ⅱ-12-n复配体系的表面化学性质进行了研究。利用正规溶液理论计算出了复配表面活性剂组分分子间的相互作用参数β^σ和β^m,研究了其增效作用情况。结果表明随着混合溶液浓度的增大,临界胶束浓度cmc值和相应的表面张力γ_cmc值随之有显著的降低。C₁₆-MADS/Ⅱ-12-n复配体系显示出比单一表面活性剂更高的表面活性。4.通过对C₁₆-MADS/K₃/AEO₉复配体系的研究表明,正规溶液理论用来处理非理想溶液中二元表面活性剂的方法,在很大程度上适于处理C₁₆-MADS/K₃/AEO₉三元表面活性剂混合体系。方法是先确定二元体系(C₁₆-MADS/K₃)的相互作用参数,再按与第三种组分AEO₉组成新的二元混合体系来进行处理。C₁₆-MADS/K₃复配体系产生最大增效作用的摩尔比为0.33:0.67,即二者等电荷比;C₁₆-MADS/K₃与AEO₉复配体系产生最大增效作用的摩尔比为7:3。另外该方法在处理三元体系时仍存在着一定的缺陷,它不能用二元体系协同作用理论对三元复配体系进行全面的解释。5.首次以C₁₆-MADS为分散剂,将纳米ZnO分散于水和陶瓷釉料中。将1-6%比例的纳米ZnO分散于水和日用陶瓷釉料中,釉料的分散性和流动性良好,施釉后釉面不开裂,解决了釉料中加入纳米ZnO而产生的团聚问题。用含有纳米ZnO的釉料施釉后,烧成品的光泽度和显微硬度明显提高,并降低了烧成温度。6.首次在较高浓度条件下,通过对C₁₆-MADS与十六烷基三甲基溴化铵（CTAB）复配溶液性质的研究,得出以下结论:在常温下,C₁₆-MADS/CATB混合体系在适当的浓度下,可形成明显的双水相,且随两个组分的比例不同,其两相的体积比呈现规律性的变化。通过偏光显微测试,其混合溶液呈现明显的晶相结构。以C₁₆-MADS与CTAB为共模板剂合成新型分子筛,将产物进行XRD、N₂吸脱附和HTEM表征,结果显示:该分子筛具有类六方孔道的双介孔分子筛（MCM-41）,孔径分别为2.2nm和3.9nm。形成的双介孔的可能机理为:由于C₁₆-MADS/CATB溶液体系形成双水相所致。在两相中两组分的浓度、两相的体积均不同。因此在溶液中形成两种分子聚集体,即形成两种胶团。在胶团结构的导向下,形成两种孔结构。另外,两相体积的不同造成两种聚集体胶团的比例不同。故最终形成两种不同尺寸的孔道分子筛,且两种孔道的比例亦不同,也无规律性地排列。更多还原

【Abstract】 Surfactants are important molleculars with double affinity.By weak mutual-function force various sequencial molleculars can be self-assembled, which have multiple significant functions.Alkyl diphenyl ether sodium disulfonate（ADPODS）is a kind of multifunctional anionic surfactants with double hydrophilic groups.As a noval type of surfactants,it has attracted remarkbale attention nowadays.In this research,a series of MADS surfactants(C₈-MADS,C₉-MADS、C₁₆-MADS)were synthesized using fatty alcohol and diphenyl ether as raw materials with alkylation-sulfonation-neutralization synthetic route.The surface activity and properties of micelle aggregation system were characterized by IR and XRD method.The return-service characterstic of the binary and ternary mixed system of C₁₆-MADS and conventional surfactants were studied, including with esterquat Gemini surfantantsⅡ-12-n（n=3,4,6）and with polyethyl eneglycol（9）mono-dodecylether（AEO₉）and dodecyldimethyl hydroxyethyl ammonium chloride（K₃）,labeled by C₁₆-MADS/Ⅱ-12-n and C₁₆-MADS/K₃/AEO₉ respectively.The interracial tension in aqueous solution and the biodegradation of these mixed surfactants were investigated as well.1.A series of alkyl diphenyl ether were synthesized with low cost raw materials,diphenyl ether and aliphatic alcohol,catalyzed by concentrated sulfuric acid,and followed by sulfonation to produce MADS.On the basis of analysis and characterization,structure of the products was identified,effect factors of the preparation reactions were investigated and the optimum reaction conditions were obtained.2.The surface chemical properties of C₈,C₉,C₁₀-MADS were determined. Experimental results indicated MADS posessed stable surface properties in inorganic acid、base or salt aqueous solutions even up to 10%mass percent.At the same time,MADS exhibited an excellent emulsifying power with a better decontamination and detergency power in hardwater than conventional sulfactants.3.The regular solution theory is entirely suitable according to the study of C₁₆-MADS/Ⅱ-12-n binary mixed system.The mixed system has synergism effect of reducing interfacial force efficency and forming micelle groups.Theγ～lgc curves was obtained by measuring interfacial force of C₁₆-MADS andⅡ-12-n aqueous solution.Thus the surface chemical properties of the system was studied.The intermolecular interaction parameters（β^σandβ^m）of surfactants were calculated through the orthodox solution theory,and the enforcement function was also researched.Results showed that critical micelle concentration（cmc）and the corresponding surface tension(γ_cmc)decreased significantly along with the increase of solution’s concentration.The C₁₆-MADS/Ⅱ-12-n mixed system revealed a higher surface activity than the single surfactant.4.Research on the C₁₆-MADS/K₃/AEO₉ showed that the method of processing binary surfactants in unperfect solutions with orthodox solution theory was mostly applicable to the tertary surfactants such as C₁₆-MADS/K₃/ AEO₉ system.Details were to determine the interaction parameter of the binary system(C₁₆-MADS/K₃),then to process the new binary system by mixing with the third ingredient AEO₉.The mole ratio when C₁₆-MADS/K₃ system could make greatest enforcement was 0.33:0.67,that was when they had equal electricity ratio,while the ratio of C₁₆-MADS/K₃/AEO₉ system was 7:3. However,the method was not so perfect when applied in tertary system for it couldn’t give a fully explaination with the cofunction theory in binary system.5.Using C₁₆-MADS as dispersant for the first time,nano ZnO was dispersed in the water and the ceramic glaze.The domestic ceramic glaze dispersed with 1-6%of nano ZnO showed good dispersibility and liquidity.The dehiscence had not appeared on the glazed ceramic surface after being doped, thus the bottleneck problem of nano ZnO agglomerating was solved.The glossiness and microhardness of the ultimate product was improved obviously, while the calcine temperature was decreased.6.In the high concentration,the C₁₆-MADS/CTAB solution had such properties that double aqueous phase would be formed apparently under a suitableconcentration,and volume ratio of the two phase showed disciplinary changes with different ratio of the two ingredients.Polarizing microscope determination showed the mixed solution had a obvious crystal phase structure. Mesoporous molecular sieves were furtherly synthesized using C₁₆-MADS and CTAB as templates.XRD,N₂ adsorption-desorption and HTEM characterization of the obtained samples showed that the obtained samples had structures similar to MCM-41 of two different mesoporous with pore diameters 2.2nm and 3.9nm. Mechanism of the two mesoporous may be atribute to the formation of double aqueous solution in the C₁₆-MADS/CATB system.The difference of the concentration and volume of the two ingredients in the two phases resulted in the formation of two molecular congeries,and two pore structures were formed induced by the two kinds of micelle group structure.Besides,volume difference of the two phase caused the ratio difference of the two micelle congeries,thus the two molecular sieves would have different size with different ratio and unregular disposion.更多还原