Surface grafted poly(ԑ-caprolactone) prepared using organocatalysed ring-opening polymerisation followed by SI ATRP Francesca Ercole, Andrew E. Rodda, Laurence Meagher, John S. Forsythe, Andrew P. Dove* Supplementary Information Materials Unless otherwise stated, all chemicals were purchased from Sigma Aldrich and used as received. All transfers of compounds for ROP (including solvents) were performed under an inert nitrogen atmosphere. ε-Caprolactone (ε-CL) and benzyl alcohol were freshly distilled into sealable ampoules from CaH 2 under an inert atmosphere and stored in a glove box at ambient temperature. Diphenyl phosphate (DPP) was powdered in a mortar and pestle and subsequently dried over P 2 O 5 in a vacuum desiccator for one week, with the P 2 O 5 replaced every day. The solid was stored in a glove box at ambient temperature. The white crystalline -BMPCL monomer, which was prepared according to a previously reported literature procedure (Mecerreyes D. et al, Macromolecules, 1999, 32, 5175-5182), was taken up in anhydrous dichloromethane (CH 2 Cl 2 ), transferred by cannula onto activated 3 Å molecular sieves and left to stand for 24 h before being transferred for a second time onto fresh 3 Å sieves and left to dry for a further 24 h. The CH 2 Cl 2 solution was then transferred to a dried Schlenk flask using a filter cannula and the CH 2 Cl 2 removed under vacuum on a vacuum manifold. The solid was left to dry under vacuum overnight. The resulting white solid was then transferred to a dry container and stored in a glove box at ambient temperature. Benzyl alcohol was distilled under reduced pressure, degassed and stored over 4 Å molecular sieves. Monomer and dried over 3 Å molecular sieves in dry CH 2 Cl 2 . Deuterated chloroform (CDCl 3 ) was purchased from Apollo Scientific Ltd was dried over 3 Å molecular sieves, flash distilled, degassed and back-filled with nitrogen, before being stored in a glove box at ambient temperature. CH 2 Cl 2 and toluene were purified over Innovative Technology SPS alumina solvent columns and degassed before use. A weak basic anion exchange resin, Amberlyst A21 (Organo Co., Ltd.) was washed with MeOH and dried in a vacuum oven overnight before use. Cu(I)Br was purified by washing 3× with glacial acetic acid, 2× with absolute ethanol and 2× with diethyl ether followed by drying in a vacuum oven overnight. Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is © The Royal Society of Chemistry 2014