Preparation of polystyrene–polyolefin multiblock copolymers by sequential coordination and anionic polymerization

Abstract

Block copolymers of polyolefins (PO) and polystyrene (PS) are attractive materials that are not synthesized directly from the olefin and styrene monomers. A strategy for construction of PS-b-PO-b-PS triblock units directly from the olefin and styrene monomers is disclosed herein. PO chains (ethylene/1-octene or ethylene/1-pentene copolymers) were grown from dialkylzinc species bearing the α-methylstyrene moiety (i.e., [4-(isopropenyl)benzyl]₂Zn) by ‘coordinative chain transfer polymerization (CCTP)’ using a typical ansa-metallocene catalyst, rac-[Me₂Si(2-methylindenyl)₂]ZrCl₂ activated with modified-methylaluminoxane (MMAO). PS chains were subsequently grown from the Zn-alkyl sites and from the α-methylstyrene moieties of the resulting PO chains by switching to anionic polymerization. When nBuLi(tmeda)₂ was fed into the system as an initiator in a quantity fulfilling the criterion [Li] > [Zn] + [Al in MMAO], nBuLi(tmeda)₂ successfully attacked the α-methylstyrene moieties to initiate the anionic styrene polymerization at both ends of the PO chains generated in the CCTP process. However, in model studies, the attack of nBuLi(tmeda)₂ on α-methylstyrene in the presence of (hexyl)₂Zn consumed two molecules of α-methylstyrene per nBuLi to afford mainly R–CH₂C(Ph)(Me)–CH₂C(Ph)(Me)Li, where R is either an nbutyl or hexyl group originating from nBuLi or (hexyl)₂Zn, respectively. This observation suggests that the block copolymer does not simply comprise the PS-b-PO-b-PS triblock, but instead comprises a multiblock containing PS-b-PO-b-PS units. The molecular weight of the polymer increased after performing anionic polymerization. Even though the phase separation of the PS and PO blocks observed in the TEM images is less regular in the multiblock copolymers, the elastomeric property of the multiblock copolymers observed in the hysteresis testing is better than that of the diblock analogue.