【作者】 朱华；

【导师】 郭建维；

【作者基本信息】 广东工业大学 ， 应用化学， 2011， 博士

【摘要】 低聚表面活性剂(oligomeric surfactant)是具有超强表面活性的一类新型表面活性剂。连接基团的结构与性质对低聚表面活性剂的性质具有较大的直接影响。金刚烷具有刚性结构,可设计性强,无毒无害等性质,以金刚烷为连接基可望赋予低聚表面活性剂诸如无毒、易升华、热稳定、抗氧化等优良性质。本文以金刚烷为原料,设计合成了一系列金刚烷基表面活性剂中间体和金刚烷基特种表面活性剂,通过IR、1H NMR和元素分析等方法表征了化合物结构。文中同时对部分关键反应进行了机理探讨和工艺优化；对所设计合成的表面活性剂进行了性能研究,探讨了结构与性能的关系。主要研究内容如下：(1)合成了四种表面活性剂关键中间体。由1-金刚烷甲酸经一锅法制备1,3-金刚烷二甲酸,收率高达92%。由1,3-二溴金刚烷直接与尿素进行胺化制得1,3-金刚烷二胺,其收率近70%。以1,3-金刚烷二甲酸为原料,经酰胺化和还原反应制得N,N,N’,N’-四甲基-1,3-二(胺甲基)金刚烷的合成路线,总收率为81%。(2)以金刚烷、氯磺酸、苯等为主要原料设计、合成了一种金刚烷基四聚磺酸盐阴离子表面活性剂—1,3,5,7-四(4-磺酸钠苯基)金刚烷。研究发现该表面活性剂不仅具有一定的表面活性(CMC=0.3 mM,γcmc=48.7 mN/m);除此之外,对聚碳酸酯具有优越的阻燃性能,是一种高效的无卤阻燃剂。(3)以金刚烷、氧化铬、溴乙酰溴、叔胺等为主要原料设计、合成了一系列含有金刚烷的三聚和四聚酯季铵盐表面活性剂。并考察了反应条件对关键步骤-氧化反应收率的影响,在各自最佳条件下,1,3,5-三羟基金刚烷和1,3,5,7-四羟基金刚烷的收率分别为50.1%和41.7%；酯化和季铵化反应收率均高于80%。并对氧化反应和酯化反应的机理进行了探讨。(4)通过环法测其表面张力发现：所合成的低聚酯季铵盐表面活性剂具有很强的表面活性,临界胶束浓度最低达到0.50 mM,γcmc最低达到37.20mN cm-1, C20最低达到0.19 mM。通过电导率法和荧光光谱测定了表面活性剂的临界胶束浓度,结果与表面张力法所得数据基本一致。考察溴化钠对CMC值和γcmc的影响,发现溴化钠能微小的降低CMC值和γcmc。另外表面活性剂的表面最大吸附量、分子头基占有最小面积、微极性、胶束聚集数、电离度等在本文中也作了报道。对不同长度疏水链和不同聚合数目表面活性剂的各指标进行了比较发现：在疏水链碳原子数在8-12范围内,疏水链越长其CMC值,Ycmc和C20越低；相同疏水链情况下,三聚表面活性剂的CMC值低于四聚表面活性剂,而四聚表面活性剂的Ycmc和C20值低于三聚表面活性剂。(5)利用振荡法测试了表面活性剂的泡沫性能,研究结果显示金刚烷基酯季铵盐表面活性剂具有很强的泡沫性能。相同疏水链情况下,四聚表面活性剂的泡沫性能较三聚表面活性剂更优,起泡性最高达到205%,5 min后稳泡性最高达到85%。利用荧光法测试了表面活性剂对芘的增溶性能,发现表面活性剂对芘具有较高的分配系数,增溶性能良好。相同疏水链情况下,三聚表面活性剂的增溶性能更强。采用分水时间法评价了表面活性剂的乳化性能,相同疏水链情况下,四聚表面活性剂的乳化性能较三聚表面活性剂更优,最大分水时间为314 min。在相同聚合度情况下,疏水链长为8-12碳原子范围内,表面活性剂的三种性能都随着碳链的延长而增强。更多还原

【Abstract】 Oligomeric surfactants are a novel family of amphiphilic compounds made up of two or more conventional surfactant "monomers" linked by spacer group(s) at the level of, or very close to the head groups. Since the hydrophobic chain will be closer and more regular than conventional surfactants, oligomeric surfactants have powerful surface activity. The diameter of adamantane molecular is 0.74 nm, which is smaller than the equilibrium distance of conventional surfactants, the properties of adamantane, such as non-toxic, sublimation, high thermal stability and resistance to oxidation, the oligomeric surfactants used adamantane as spacer may possess some excellent performance. In this thesis, the design, synthesis and properties of some degradable oligomeric surfactants based on adamantane are studied. Furthermore, some mechanisms of some key reactions were discussed, the reaction condition were optimized. All of the key intermediates and surfactants were characterized by IR,1H NMR and elemental analysis.(1) Some key intermediates,1,3-adamantanedicarboxylic acid, 1,3-di am ino adamantane, N, N,N’,N’-tetramethy 1-1,3-bis(amino methyl)-adamantane, 1,3-bis(chloromethyl)adamantane, were synthesized for the purpose of produce oligomeric surfactants. Under the optimum condition, the (total) yield of 1,3-adamantanedicarboxylic acid,1,3-diaminoadamantane, N,N,N’,N’-tetramethyl-1,3-bis(aminomethyl)adamantane, 1,3-bis(chloro-methyl)-adamantane were 92%,72%,81%,27.1%.(2) An tetra sulfate substitute-adamantane surfactants,1,3,5,7-tetrakis (4-sodium sulfate phenyl) adamantane, was designed and synthesized from adamantane, benzene and chlorosulfonic acid. The CMC value andγcmc of this surfactant were 0.3 mM and 48.7 mN/m, respectively. This compound is an efficient halogen-free flame retardant also. (3) A series of adamantane based degradable oligomeric (trimeric and tetrameric) quaternary ammonium surfactants were synthesized from adamantane, chromium trioxide, bromoacetyl bromide and tertiary amine. The oxidation reaction was optimized. Under the optimum conditions, the yields of 1,3,5-trihydroxyadamantane and 1,3,5,7-tetrahydroxy-adamantane were 50.1%and 41.7%, respectively. The yields of esterification and quaterisation reaction were more than 80%. The mechanisms of oxidation and esterification reaction were discussed.(4) Surface tension data which had been achieved by ring-method, showed that the oligomeric surfactants had strong surface activity, the CMC values andγcmc of the oligomeric surfactants reached 0.50 mM and 37.20 mN cm-1, respectively. The CMC values were tested by conductivity and fluorescence method, the results had paralleled with the surface tension method. The CMC values andγcmc of these surfactants are less affected by NaBr. C20,Γm, amin, micro-polarity (ε), micelle aggregation number (N) and micelle ionizability (β) of surfactants was reported. Influences of length of hydrophobic chain and oligomerization degree on the properties of surfactants were investigated, the results shown that longer chain had better performance (The carbon atoms of hydrophobic chains was between 8-12); trimeric surfactants had smaller CMC values than tetrameric surfactants, theγcmc and C20 of tetrameric surfactants were lower than trimeric surfactants.(5) The foam properties, solubilization and emulsification of the surfactants were investigated. It showed that, surfactants had good to excellent foaming property; the Kmc (mole fraction micelle-phase /aqueous-phase partition coefficient) was tremendous, the negative free energy of transfer indicated the process of solubilizates transfered from the aqueous phase into the micellar pseudophase was favorable and spontaneous; the emulsification properties of these surfactants were better than the conventional and Gemini surfactants which had same hydrophobic chain.更多还原