Preparation of One‐Dimensional Polymer Brushes by Atom Transfer Radical Polymerization of Styrene Initiated by Macroinitiator

ABSTRACT Reversible deactivation radical polymerization (RDRP) is a controllable technique for free radical polymerization to synthesize polymer brushes. Macroinitiators have the advantage of grafting polymer brushes with high density over small molecule initiators due to the multiple active units in one molecule. However, there are still some shortcomings in the control of catalytic activity and polymer structure due to the unique segmental motion of macromolecules. In this work, we prepared one‐dimensional styrene polymer brushes via the atom transfer radical polymerization (ATRP) method using chlorinated polybutadiene (Cl‐LBR) as a macroinitiator and cuprous chloride (CuCl) as a catalyst. The effect of polymerization conditions on catalytic activity and polymer structure was investigated in detail. The ligands for CuCl including 2,2‐bipyridine (bpy) and pentamethyl‐diethylenetriamine (PMDETA) were also examined. Additionally, l‐ascorbic acid was adopted as a reducing agent to generate activator regenerated electron transfer (ARGET) ATRP in Cl‐LBR initiated system. In comparison with ATRP, ARGET ATRP can reduce the dosage of CuCl by 20 times. This work prepared one‐dimensional polystyrene polymer brushes with high polymerization rate and controllable structure through macromolecular initiators. This method provides a promising pathway for the preparation of one‐dimensional polymers with functional designs and demonstrates broad developmental potential in antifouling.