原子转移自由基聚合法合成PS-g-PMMA

以氯乙酰化聚苯乙烯微球（PS-acyl-Cl）为大分子引发剂，甲基丙烯酸甲酯（MMA）为单体，CuCl/CuCl₂及N，N，N′，N′-四甲基乙二胺（TMEDA）为催化体系的原子转移自由基聚合反应，成功在PS-acyl-Cl表面接枝上PMMA分子链而获得聚苯乙烯 接枝 聚甲基丙烯酸甲酯（PS-g-PMMA）。考察了催化剂、反应温度、溶剂用量等条件对接枝反应的影响，优化的反应条件下，使用氯乙酰基担载量3.44 mmol.g^-1的PS-acyl-Cl，15 h可获得增重率687% 的PS-g-PMMA，且反应表现出一级动力学特征（k=513×10^-5 s^-1）。通过改变反应条件，可得到不同PMMA接枝链长的PS-g-PMMA。反应得到的PS-g-PMMA经水解后有望作为高担载量弱酸型离子交换树脂或进一步功能化后作为酶的柔性固定化载体。

Preparation of PS-g-PMMA via atom transfer radical polymerization

Polystyrene grafted with poly（methyl methacrylate（PS-g-PMMA）has been achieved via atom transfer radical polymerization（ATRP）methodologyThe grafting reaction of methyl methacrylate（MMA）was initiated from the chloroacetyl groups on the chloroacetyl styrene divinylbenzene copolymer microspheres（PS-acyl-Cl）with CuCl/CuCl₂ and N，N，N′，N′-tetramethyl ethylenediamine（TMEDA）complex as catalystThe influences of the catalyst，reaction temperature，and the amount of ligand and solvent on the grafting reaction were investigatedUnder the optimized conditions，satisfactory grafting yields（up to 687% within 15 h）were obtained using PS-acyl-Cl microspheres with 3.44 mmol.g^-1 of chloroacetyl groups，and at the same time，the grafting reaction showed a first order kinetics nature（k=5.13×10^-5 s^-1）.The PS-g-PMMA microspheres with different grafting arm lengths were obtained by varying the reaction conditions，which are expected to be used as weak acid ion exchange resin with high loading amount after being hydrolyzed，or as flexible immobilization carrier for enzymes after further functionalization.