Styrene Moiety-Carrying Diorganozinc Compound Preparation for Polystyrene-Poly(ethylene-co-1-hexene)-Polystyrene Triblock Copolymer Production

Abstract

Polystyrene (PS)-block-poly(ethylene-co-1-butene)block-PS (SEBS), produced by PS-block-polybutadiene-block-PS hydrogenation, is a high-performance thermoplastic elastomer. Hydrogenation is costly and tedious, making SEBS market expansion difficult. Thus, we envisioned a new one-pot SEBS-like triblock copolymer synthetic scheme to grow PO chains from styrene moiety-carrying diorganozinc compounds by coordinative chain transfer polymerization (CCTP), followed by anionic styrene polymerization using a specially designed initiator, allowing PS chain growth from not only the styrene moieties but also the Zn−C sites. Large-scale preparation of highly pure styrene moiety-carrying diorganozinc compounds was one of the main challenges we faced, but we overcame it by synthesizing (CH 2 CHC 6 H 4 CH 2 CH 2 CH 2 ) 2 Zn (4), a stable and crystalline solid that worked well as a CCTP agent. This enabled the preparation of PS-block-poly(ethylene-co-1-hexene)-block-PS (SEHS), which exhibited a stress−strain curve similar to that of the commercial-grade SEBS. The SEHS dispersed better in a polypropylene (PP) matrix, allowing it to act as a better toughening agent for PP blending than the commercial-grade SEBS. Moreover, SEHS was less viscous, exhibiting better workability.

Breath‐Figure Self‐Assembled Low‐Cost Janus Fabrics for Highly Efficient and Stable Solar Desalination

“…After the CB@SBS/cotton fabric is taken out from the high‐humidity environment, the water droplets on the surface can volatilize spontaneously, forming pores of different sizes. [ 47–53 ]…”

Design of selective divalent chain transfer agents for coordinative chain transfer polymerization of ethylene and its copolymerization with butadiene

“…M' is a main group metal or zinc As a controlled polymerization technique, CCTP potentially allows the production of end-functional polyolefins, [17][18][19] telechelic polyethylenes, 20,21 and block copolymers. [22][23][24][25][26][27] Employing a polymetalated CTA based on zinc, Lee and col. took the advantage of CCTP to control the copolymerization of ethylene with propylene using a pyridylamido hafnium Please do not adjust margins Please do not adjust margins complex. 24 The oxidation of the chains bound to zinc allows a straightforward functionalization of produced polyolefins.…”

“…15,16 As a controlled polymerization technique, CCTP potentially allows the production of end-functional polyolefins, [17][18][19] telechelic polyethylenes, 20,21 and block copolymers. [22][23][24][25][26][27] Employing a polymetalated CTA based on zinc, Lee and coll. took the advantage of CCTP to control the copolymerization of ethylene with propylene using a pyridylamido hafnium complex.…”

Switch from Anionic Polymerization to Coordinative Chain Transfer Polymerization: A Valuable Strategy to Make Olefin Block Copolymers

“…showed that di‐hexylzinc was able to initiate an anionic polymerization of styrene in the presence of n ‐butyllithium ( n BuLi) and N,N,N′,N′‐tetramethylethylenediamine (TMEDA) although side initiation with n BuLi was taking place [26] . They extrapolate this result to the reactivation of PO chains produced by CCTP mediated by organometallic zinc compounds to implement the switch from CCTP to anionic polymerization and produce PO‐ b ‐PS [26] and PS‐ b ‐PO‐ b ‐PS block copolymers [27] . As shown in the model experiments conducted with molecular dialkylzinc, this strategy is however associated with the formation of homopolymer formed during the anionic polymerization.…”