School of Chemical and Material Engineering, Jiangnan University, Lihu Road 1800, Wuxi 214122, PR China.
Int J Biol Macromol. 2011 Jan 1;48(1):210-4. doi: 10.1016/j.ijbiomac.2010.11.007. Epub 2010 Nov 18.
Trimethylsilylated hydroxyethyl cellulose (TMSHEC) was synthesized by using hexamethyldisilazane (HMDS) as silylated agent. With the partial protection of hydroxyl groups of HEC by silylation, the novel poly(ɛ-polycaprolactone) (PCL) grafted HEC (HEC-g-PCL) copolymers were successfully prepared by homogenous ring-opening graft polymerization and deprotection procedure. The structure of HEC-g-PCL copolymers was characterized by FTIR and 1H NMR. Fluorescence spectrum of HEC-g-PCL copolymer dilute solution indicated that copolymers could associate and form hydrophobic microdomains in aqueous solution. With the increasing of grafted PCL content, the critical association concentration (cac) of HEC-g-PCL copolymers decreased. The surface tension of HEC-g-PCL copolymers decreased dramatically with the increasing of the concentration and then approached to a plateau value when concentration was above the cac of HEC-g-PCL copolymers. The hydrodynamic radius of the aggregate of copolymer in dilute solution was found to increase with the increasing of the grafted PCL content. When the concentration of copolymer was above the cac, the zero-shear viscosity of the copolymer increased sharply and became much higher than that of HEC at the same concentration.
采用六甲基二硅氮烷(HMDS)作为硅烷化试剂,合成了三甲基硅烷化羟乙基纤维素(TMSHEC)。通过硅烷化对 HEC 的部分羟基进行保护,通过均相开环接枝聚合和脱保护反应,成功制备了新型聚(ε-己内酯)(PCL)接枝羟乙基纤维素(HEC-g-PCL)共聚物。用傅里叶变换红外光谱(FTIR)和核磁共振氢谱(1H NMR)对 HEC-g-PCL 共聚物的结构进行了表征。HEC-g-PCL 共聚物稀溶液的荧光光谱表明,共聚物在水溶液中可以缔合形成疏水性微区。随着接枝 PCL 含量的增加,HEC-g-PCL 共聚物的临界聚集浓度(cac)降低。随着浓度的增加,HEC-g-PCL 共聚物的表面张力急剧下降,当浓度高于 HEC-g-PCL 共聚物的 cac 时,表面张力趋于平台值。在稀溶液中,共聚物聚集体的流体力学半径随接枝 PCL 含量的增加而增加。当共聚物浓度高于 cac 时,共聚物的零剪切粘度急剧增加,且在相同浓度下远高于 HEC。