【作者】 徐冬梅；

【导师】 朱秀林； 张可达；

【作者基本信息】 苏州大学 ， 有机化学， 2004， 博士

【摘要】 本论文设计合成了一系列树枝状大分子，并对其进行了表征和功能化，考察了树枝状大分子及其功能化产物的性能，并进行了将其作为功能性材料的应用尝试。 树枝状大分子的合成： 本论文首次采用三官能度的三羟甲基丙烷三丙烯酸酯和四官能度的乙二胺为单体（A₃-B₄体系），通过Michael加成反应，分别合成了以乙二胺（或三羟甲基丙烷三丙烯酸酯）为核，以聚（酯—胺）为骨架的1代和2代端丙烯酸酯基树枝状大分子G1.0（acrylate）₈和G2.0（acrylate）₄₈，以及1代和1.5代端氨基树枝状大分子G1.0（NH₂）₃和G1.5（NH₂）₈。反应在温和的条件下进行，采用支化单体过量的方法抑制副反应，提高树枝状大分子的产率。结果以较高产率得到目标产物。 用本方法合成树枝状大分子，仅采用了一种具有原子经济性的反应，即Michael加成反应。两种单体交替反应，省去了繁琐的官能团保护及解保护步骤，每一步反应都使树枝状大分子有效增长。端丙烯酸酯基与端氨基隔代交替生长。两种单体都带有多官能团，既能作核又能作支化单体，所得树枝状大分子的端基增长非常迅速，以乙二胺为核的第2代树枝状大分子就含有48个端丙烯酸酯基。丙烯酸酯基及氨基很容易转化成其他官能团，因此本论文设计合成的树枝状大分子表面很容易进一步功能化。 树枝状大分子的分离： 分离纯化是树枝状大分子制备中遇到的最大困难，而以乙二胺为核的第1代端丙烯酸酯基树枝状大分子G1.0（acrylate）₈和第1.5代端氨基树枝状大分子G1.5（NH₂）₈，以及以三羟甲基丙烷为核的第1代端氨基树枝状大分子G1.0（NH₂）₃能根据其与所在体系中其他成分在选择性溶剂中的溶解度不同，通过用选择性溶剂萃取的方法进行分离纯化。 本分离方法的特点是：简单，能获得较大量产物，且产物纯度较高。 树枝状大分子的功能化：端丙烯酸酷基及端氨基树枝状大分子的合成、表征及功能化摘要 羚基化:将第l代端丙烯酸酷基树枝状大分子Gl.0（acrylate），轻基化。Gl.0（acrylate）:与二乙醇胺在甲醇溶液中进行Michael加成反应得到16个端轻基的树枝状大分子Gl.O（0H）16。反应条件温和，不需要复杂的分离纯化过程，反应结束减压除去甲醇就能得到产率和纯度都较高的产物。 磺化:将G一。（aerylate）、磺化。GI.o（aeryzate），与NaHso:、以丁酮和一缩二乙二醇混合物为溶剂反应得到外围带8个磺酸钠基团的树枝状大分子GI.O（S仇Na），。实现了在常压及有机溶剂中将树枝状大分子外围多个丙烯酸酷双键同时进行磺化，成功进行了有机磺酸钠盐的分离纯化。树枝状大分子的结构表征: 用IR、’H NMR，’3C NMR、元素分析、HPLC和ESI一MS等方法对所得树枝状大分子及其功能化产物的结构进行了表征。树枝状大分子的性能及应用: 水溶性树枝状大分子的溶液行为:水溶性树枝状大分子GI.0（NH2）3、GI.5（NHZ）:、Gl.0（OH）:6、GI.0（S03Na）。都是表面活性剂。相同浓度水溶液表面张力均低于相似分子量聚乙二醇水溶液的表面张力。GI.0（NHZ），、Gl.5（NHZ）。水溶液表面张力随浓度增大的变化趋势类似于聚乙二醇，而Gl.O（OH）:。、GI.0（S认Na），在较低浓度时就能显著降低表面张力。 树枝状多磺酸钠GI.O（S氏Na）。是一种性能独特的聚电解质:其水溶液表现为胀塑性流体。浓度为1.0%一5.0%的Gl，O（S氏Na）:水溶液粘度在pH值1.5一12.0、电导率在pH值3.0¹0.0范围内非常稳定，说明这种电解质可以在宽的pH值范围内使用。GI.0（S仇Na），水溶液粘度与浓度的关系与小分子NaCI相似，而电导率随浓度的变化与高分子海藻酸钠相似。 Gl.O（S仇Na），在水中能以弱的分子间力形成球形聚集体。 水溶性树枝状大分子与金属离子的作用:在稀的水溶液中，树枝状大分子GI.0（OH），。、Gz.0（50二、Na），与金属离子Ag‘、CuZ‘、FeZ’之间能通过配位或静电作用形成稳定的复合体系，这是树枝状大分子用作纳米反应器的基础。在浓的水溶液中，端丙烯酸酷基及端氨基树枝状大分子的合成、表征及功能化摘要GI.0（S岛Na）:与HZPdCI;能形成由球形聚集体组成的树枝状聚集体。 树枝状大分子用作紫外光固化齐聚物:Gl.0（acrylate）:用作紫外光固化齐聚物，与相似分子量线性脂肪族聚氨酷丙烯酸酷树脂相比，粘度小，固化速度快。且固化产物硬度高，耐溶剂性好。 由于众多丙烯酸酷双键集中于同一个体积庞大的树枝状大分子上，G2.0（aerylate）月、中双键的聚合活性下降，含GZ.O（aerylate）。、的紫外光固化体系固化速度比Gl.。（aCrylate）:体系和线性脂肪族聚氨酷丙烯酸酷体系慢。 通过FTIR跟踪研究了GI .0（aCrylate），体系固化过程中双键的变化规律和活性稀释剂、光引发剂等对双键转化率的影响。 树枝状大分子用作环氧树脂固化剂:将GI.0(NH办.和Gl.5（NH2）。作为环氧树脂固化剂，挥发性小，毒性小，易与环氧树脂混合。与EDA/环氧树脂体系相比，Gl.0（NHZ），/环氧树脂体系和Gl.5（NHZ），/环氧树脂体系适用期和凝胶时间长，而加热时固化速度快。DSC分析表明G 1 .0（NHZ）3和Gl.5（NHZ）。作为固化剂的体系在固化过程中分2阶段逐渐放热，放热过程比更多还原

【Abstract】 A series of Poly (ester-amine) dendrimers were synthesized, characterized and functionalized. Properties of dendrimers and functional dendrimers were studied, and some dendrimers were tried for functional materials.SYNTHESIS OF DENDRIMERS:For the first time. Poly (ester-amine) dendrimers with ethylene diamine (EDA) or trimethylolpropane triacrylate (TMPTA) as a core, acrylate or amino as a terminal group were synthesized from TMPTA (three functional groups) and EDA (four functional groups) by Michael addition reaction. The reactions were carried out under mild conditions to give dendrimers in moderate yields. The by-reactions were suppressed by use of excess branching monomers.In the synthesis, only one atomic economical reaction (Michael addition reaction) was employed. Two monomers reacted alternatively without protect-deprotect steps so that each step reaction made the dendrimers grow efficiently. The terminal acrylate group and amino grew rapidly in turn because both of the monomers contained multifunctional groups. For example, there were 48 terminal acrylate groups on the periphery of the second-generation dendrimer with EDA as a core and TMPTA as a branching monomer. Both acrylate and amino could be easily changed into other functional groups. Therefore, dendrimers with peripheral acrylate and amino could be easily further functionalized.SEPARATION OF DENDRIMERS:The dendrimer Gl.O (NH2)3 (with TMPTA core and amino terminal group), Gl.O (acrylate)8 (with EDA core and acrylate terminal-group), and G1.5 (NH2)g (with EDA core and amino terminal group) could be separated and purified by extraction with solvents. This separation method was simple and could get products with high purities.FUNCTIONALIZATION OF DENDRIMERS:HydrOXylation: Gl.O (acrylate)8 was hydroxylated with diethanolamine (DBA) by Michael addition reaction under mild reaction conditions to form hydroxyl terminated dendrimers Gl.O (OH)i6 which could be separated in a quantitative yield and high purity by removal of methanol after the reaction had finished.Sulfonation: Sulfonation of 8 acrylate double bonds on the periphery of Gl.O (acrylate)g with NaHSCb was carried out in organic mixture solvent of diglycol and 2-butanone under normal pressure. The sulfonafe sodium-terminated dendrimer Gl.O (SOaNaJg was successfully isolated easily.CHARACTERIZATION OF DENDRIMERS:The structures of dendrimers and their functional products were characterized by FTIR, ’H NMR, I3C NMR, elemental analysis, HPLC and ESI-MS.PROPERTIES AND APPLICATION OF DENDRIMERS:Performance of water-soluble dendrimers in solution: Water-solubledendrimers Gl.O (NH2)3, G1.5 (NH2)g, Gl.O (OH)i6 and Gl.O (SO3Na)8 acted as surfactants. The surface tension of their water solutions was lower than that of polyethylene glycol (PEG) aqueous with the same concentration. When the concentration of aqueous increased, the surface tension of Gl.O (NHi^, G1.5 (NH2)s and PEG aqueous gradually decreased, while the surface tension of Gl.O (OH)i6 and Gl.O (SO^Na^ aqueous greatly decreased at first, then gradually tended to stable.Gl.O (SO3Na)g dendrimer was a polyelectrolyte with unique properties. Its aqueous appeared as dilatant fluid. The viscosity of 1.0% ?.0% aqueous was almost no change in the range of PH value from 1.5 to 12.0, and electric conductivity of the aqueous changed very little from the PH value 3.0 to 10.0, which indicated that Gl.O (SO3Na)g could be applied in the wide range of pH value.The effect of concentration on the viscosity of Gl.O (SC>3Na)g aqueous was similar to that of NaCl aqueous, while the effect of concentration on electric conductivity of Gl.O(SO3Na)g aqueous was similar to that of Alginate sodium. Gl.O (SO3Na)g could form global aggregates in water.Interaction of water-soluble dendrimers with metal ion: in dilute aqueous,Gl.O (OH),6 and Gl.O (SO3Na)8 dendrimers interacted with Ag+, Cu2+, Fe2+ by intermolecular force or electrostatic attraction, leading to stable dendrimer / metal ions composites which was the basis o更多还原