超支化聚硅碳烷-g-环糊精聚合物刷的合成与表征

STNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLYCARBOSILANE-g-CYCLODEXTRIN POLYMER BRUSHES

通过硅氢加成反应和核多步法聚合合成出超支化聚硅碳烷(HBP),并对其端基进行了硅氢化、羟基化和酰氯化三步改性得到大分子引发剂HBP-Cl;再用其引发甲基丙烯酸N,N-二甲氨基乙酯(DMA)进行原子转移自由基聚合(ATRP),得到超支化聚硅碳烷-g-聚甲基丙烯酸N,N-二甲氨基乙酯(HBP-g-PDMA),最后将单-6-碘代β-CD通过离子键固载到PDMA链上,得到超支化聚硅碳烷-g-环糊精聚合物刷(HBP-g-PDMA-β-CD).采用FTIR、1H-NMR、13C-NMR、29Si-NMR对其结构进行了表征,利用凝胶渗透色谱/多角度激光光散射(SEC/MALLS)联用仪和激光粒度分析仪研究了其高分子的精细结构,并通过元素分析研究了固载时间对β-CD固载量的影响.

Hyperbranched polycarbosilane-g-β-cyclodextrin （β-CD） polymer brushes based on carbosilane core were synthesized. At first, hyperbranched polycarbosilanes （HBP） with carbosilane cores of 3 to 5 generations were prepared via hydrosilylation addition and pseudo-one-step using methyldiallylsilane as monomer （AB2 ） and 1,2-bis （diallyl（methyl） silyl） ethane as core （ B4 ）, respectively. Then, HBP was modified by 1,1,3,3-tetrmethyldisiloxane, allyl alcohol and chloroacetyl chloride for obtaining hyperbranched polycarbosilanes carrying chloride atoms （HBP- C1）. It may which act as a macroinitiator for further polymerization of a hyperbranched polymer with functional arms. For this purpose, HBP-g-poly（ N, N-dimethylaminoethyl methacrylate） （PDMA） with different arm length was synthesized by atom transfer radical polymerization （ATRP）. Finally, HBP-g-PDMA-β-CD with functional polymer brushes was obtianed by immobilization of Mono-6-I-β-CD onto PDMA chains. Their macromolecular structures were characterized by FTIR,^1H-NMR,^13C-NMR and 29Si-NMR. In addtion, the macromolecular architecture of HBP-g- PDMA-β-CD, including the inner HBP structure with carbosilane core and the exterior PDMAEMA layer, was confirmed by SEC/MALLS and particle size analyses. Besides, it was found that the amount of β-CD content incorporating onto PDMA segments can also be regulated by changing reaction time.