末端带有溴甲基基团的柱状树枝化聚酰胺的合成与表征  

SYNTHESIS AND CHARACTERIZATION OF A DENDRONIZED POLYAMIDE WITH BROMOMETHYL GROUPS IN THE PERIPHERY

作　　者：苗艳茹[1] 徐伟箭[1] 刘美华[1] 俞霞[1] 朱林英 熊远钦[1] 

机构地区：[1]化学/生物传感和化学计量学国家重点实验室湖南大学化学化工学院,长沙410082

出　　处：《高分子学报》2008年第3期292-296,共5页Acta Polymerica Sinica

基　　金：湖南大学化学/生物传感和计量学国家重点实验室开放基金(基金号200603)资助项目

摘　　要：采用大分子单体的方法合成了一种含大量溴甲基官能团端基,主链和侧链均为聚酰胺的功能化柱状树枝化聚酰胺.氯化亚砜的新活化工艺使整个合成过程不需要保护和去保护的步骤且减少了副反应的产生,从而使得合成和纯化更加简单.产物的结构通过红外和核磁得到了证实.由分子量测试知,聚酰胺的重均分子量(Mw)为5.01×104,分子量分布为2.74.由溶解性测试知,该聚合物能溶解于N,N′-二甲基甲酰胺、N,N′-二甲基乙酰胺、二甲亚砜、1-甲基-2-吡咯烷酮和硫酸等溶剂,溶解性能得到了大大的提高,主要是由于侧链树枝化单元和末端溴甲基存在的缘故.由粘度测试知,该聚酰胺的粘度低,主要是由于侧链树枝化单元的屏蔽效应.该聚合物的热性能也由TGA测试得到了表征,结果表明该聚酰胺具有良好的热性能.由于该聚酰胺外端具有大量的溴甲基基团,它可以作为原子转移自由基聚合反应的引发剂来合成大型的梳形聚合物,另外通过把它外围的溴甲基转化为其它的功能化基团,可以使它应用于其它更广的领域.A novel functionalized dendronized polyamide decorated with a lot of bromomethyl groups in theperiphery has been reported by the macromonomer route. The resulting polyamide had both a polyamide backbone and polyamide dendrons. A new activating procedure of thionyl chloride as an activating agent was adopted to synthesize the dendrons, macromonomer and polyamide. This activating procedure eliminated the protection/deprotection procedure and reduced side reactions. The syntheses of the products adopted the method of the convergent synthesis which was carried out by a two-step method involving 1 the activation of carboxylic groups withthionyl chloride and 2 condensation with an unprotected AB2 building block. The structures of the products were confirmed by Fourier transform infrared and NMR spectral analyses. The gel permeation chromatography analyses （GPC） of the resulting polyamide showed a typical weight-average molecular weight （Mw） of 5.01 × 10^4 versus polystyrene and a polydispersity of 2.74. The solubility of the resulting polyamide was improved remarkably because of the introduction of the dendritic fragments and the existence of the periphery functional groups. The resulting polyamide could easily dissolve in aprotie polar solvents such as N,N-dimethylformamide （DMF）,N, N-dimethylacetamide （DMAc）, dimethyl sulfoxide （DMSO）, N-methyl-2-pyrrolidone （NMP） and sulfuric acid （H2SO4 ）. The inherent viscosity of the resulting polyamide was low because of the presence of the dendritic fragments, and it was 0.09 dL/g. The thermal properties were also studied by thermogravimetric analysis （TGA）, and the result showed that the resulting polyamide had good thermal properties. Because of a lot of bromomethyl groups in the periphery, the resulting polyamide could be used as a initiator for atom transfer radical polymerization （ATRP） to synthesize ＂hairy＂ functional derivatives and could also be applied in many fields through converting bromomethyl groups into other desired group

关 键 词：功能化 柱状树枝化聚酰胺 氯化亚砜 溴甲基基团 

分 类 号：O633.22[理学—高分子化学]