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Polymers 2017, 9(10), 481; https://doi.org/10.3390/polym9100481

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

Department of Molecular Science and Technology, Ajou University, Suwon 443-749, Korea
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Received: 28 August 2017 / Revised: 19 September 2017 / Accepted: 29 September 2017 / Published: 2 October 2017
(This article belongs to the Special Issue Olefin Polymerization and Polyolefin)
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Abstract

Triblock copolymers of polystyrene (PS) and a polyolefin (PO), e.g., PS-block-poly(ethylene-co-1-butene)-block-PS (SEBS), are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH2)2Zn) was prepared, from which poly(ethylene-co-propylene) chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta) (pmdeta = pentamethyldiethylenetriamine). We found that the fraction of the extracted PS homopolymer was low (~20%) and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa). Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS. View Full-Text
Keywords: coordinative chain transfer polymerization; di-end-functional polyolefin; block copolymer; thermoplastic elastomer coordinative chain transfer polymerization; di-end-functional polyolefin; block copolymer; thermoplastic elastomer
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Kim, C.S.; Park, S.S.; Kim, S.D.; Kwon, S.J.; Baek, J.W.; Lee, B.Y. Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers. Polymers 2017, 9, 481.

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