| Abstract: | Polyethylene (PE)‐based 3‐ and 4‐miktoarm star PE(PCL)2, PE(PCL)3] and H‐type (PCL)2PE(PCL)2] block copolymers polycaprolactone (PCL)] were synthesized by a combination of polyhomologation, chlorosilane chemistry, and ring opening polymerization (ROP). The following steps were used for the synthesis of the miktoarm stars: (a) reaction of a hydroxy‐terminated polyethylene (PE‐OH), prepared by polyhomologation of dimethylsulfoxonium methylide with a monofunctional boron initiator followed by oxidation/hydrolysis, with chloromethyl(methyl)dimethoxysilane or chloromethyltrimethoxysilane; (b) hydrolysis of the produced ω‐di(tri)methoxysilyl‐polyethylenes to afford ω‐dihydroxy‐polyethylene (difunctional initiator) and ω‐trihydroxy‐polyethylene (trifunctional initiator); and (c) ROP of ?‐caprolactone with the difunctional (3‐miktoarm star) or trifunctional macroinitiator (4‐miktoarm star), in the presence of 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2λ5,4λ5‐catenadi(phosphazene) (t‐BuP2). The H‐type block copolymers were synthesized using the same strategy, but with a difunctional polyhomologation initiator. All intermediates and final products were characterized by HT‐GPC, 1H NMR and FTIR analyses. Thermal properties of the PE precursors and all final products were investigated by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2129–2136 |
