摘要
在Cu Cl/bpy催化体系下,通过对氯甲基苯乙烯(CMS)自引发制得球状超支化聚对氯甲基苯乙烯(h-PCMS),再以h-PCMS作为大分子引发剂,通过两步原子转移自由基聚合(ATRP)成功在球状h-PCMS表面接枝二嵌段聚合物聚甲基丙烯酸乙酯-b-聚甲基丙烯酸甲酯(PEMA-b-PMMA),合成了星状多臂共聚物h-PCMS2700-g-PEMA41000-b-PMMA15000(下标为分子量),分子量分布为1. 6,其结构和性能经1H NMR、IR、GPC和DSC表征。通过1H NMR定量分析表明,h-PCMS中的苄基氯具有活性,可进一步引发接枝反应,次苄基氯不能引发ATRP反应。在每一个h-PCMS表面有接近三分之一的苄基氯参与接枝反应,接枝臂数为6。
Spherical hyperbranched poly( chloromethyl styrene)( h-PCMS) was prepared by self-initiated polymerization of chloromethyl styrene( CMS) catalyzed by CuCl/bpy. A two-block polymer,polymethyl methacrylate-b-polymethyl methacrylate( PEMA-b-PMMA),was grafted on the surface of h-PCMS by two steps of atom transfer radical polymerization( ATRP) initiated by h-PCMS,to afford the star-shaped multi-arm copolymers h-PCMS2700-g-PEMA41000-b-PMMA15000( subscripts refering to molecular weight),the molecular weight distribution is about 1. 6. The structure and properties were characterized by1 H NMR,IR,GPC and DSC. It was confirmed by1 H NMR that benzyl chloride in h-PCMS was active,which could lead to further graft reaction,and secondary benzyl chloride could not initiate ATRP reaction. Approximately one-third of the benzyl chloride was involved in the grafting reaction on each h-PCMS surface resulting in a graft arm number of 6.
引文
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