Synthesis of amphiphilic macrocyclic graft copolymer consisting of a poly(ethylene oxide) ring and multi-poly(ɛ-caprolactone) lateral chains

Abstract

A series of amphiphilic macrocyclic graft copolymers composed of a hydrophilic poly(ethylene oxide) as ring and hydrophobic poly(ɛ-caprolactone) as lateral chains with different grafting lengths and densities of side chains were prepared by a combination of anionic ring-opening polymerization and coordination–insertion ring-opening polymerization. The anionic ring-opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out first using triethylene glycol and diphenylmethyl potassium (DPMK) as co-initiators, and a linear α,ω-dihydroxyl poly(ethylene oxide) with pendant protected hydroxymethyls (l-poly(EO-co-EEGE)) was obtained. The monomer reactivity ratios of these compounds are r1(EO)=1.20±0.01 and r2(EEGE)=0.76±0.02, respectively. Then the ring closure of l-poly(EO-co-EEGE) was achieved via an ether linkage by reaction with tosyl chloride (TsCl) in the presence of solid KOH. The crude cyclized product containing the linear chain-extended polymer was hydrolyzed in acidic conditions first and then purified by treating with α-CD. The pure cyclic copolymer of EO and glycidol (Gly) with multipendant hydroxymethyls [c-poly(EO-co-Gly)] as the macroinitiator was used further to initiate the ring-opening polymerization of ɛ-caprolactone (CL), and a series of amphiphilic macrocyclic graft copolymers c-PEO-g-PCL were obtained. The final products and intermediates were characterized by GPC, NMR and MALDI-TOF in detail.