Synthesis of miktoarm star (block) polymers based on a heterofunctional initiator via combination of ROP, ATRP and functional group transformation

Versatile miktoarm three-arm star polymers, (polystyrene)(polyε-caprolactone)2 ((PS)(PCL)2), (PS-b-poly(n-butyl acrylate))(PCL-b-PS-b-poly(n-butyl acrylate))2 ((PS-b-PnBA)(PCL-b-PS-b-PnBA)2) and (PtBA-b-PS)(PCL-b-PtBA-b-PS)2 were synthesized via combination of atom-transfer radical polymerization (ATRP), functional group transformation technique and ring opening polymerization (ROP) using 1,1-dihydroxymethyl-1-(2-bromoisobutyryloxy)methyl ethane (DHB) as a heterofunctional initiator. In the synthesis of (PS)(PCL)2 by combination of ROP of ε-caprolactone (ε-CL) and ATRP, the implementation sequence, ROP followed by ATRP, was proved to be effective to get a well-defined miktoarm star polymer than the reverse one. The two miktoarm star block polymers, (PS-b-PnBA)(PCL-b-PS-b-PnBA)2 and (PtBA-b-PS)(PCL-b-PtBA-b-PS)2, were prepared by one ROP step, one group transformation and ATRP steps using the same initiator. All the polymers have defined structures and their molecular weights are adjustable with good controllability.