A rhodium‐based multicomponent catalytic system for well‐controlled living polymerization of phenylacetylenes has been developed. The catalytic system is composed of readily available and bench‐stable [Rh(nbd)Cl]2, aryl boronic acid derivatives, diphenylacetylene, 50 % aqueous KOH, and PPh3. This system offers a method for the facile and versatile synthesis of various end‐functionalized cis‐stereoregular poly(phenylacetylene)s because components from aryl boronic acids and diphenylacetylene were introduced to the initiating end of the polymers. The polymerization reaction shows a typical living nature with a high initiation efficiency, and the molecular weight of the resulting poly(phenylacetylene)s can be readily controlled with very narrow molecular‐weight distributions (Mw/Mn=1.02–1.09). The experimental results suggest that the present catalytic system has a higher polymerization activity than the polymerization activities of other rhodium‐based catalytic systems previously reported.

Various α,β-unsaturated carbonyl compounds, such as acrylates and acrylamides, were quantitatively introduced to the terminal chain end of poly­(phenylacetylene)­s by C–C bond formation with terminal organorhodium­(I) species formed in the living polymerization of phenylacetylenes with a rhodium-based multicomponent catalytic system that we have recently developed, when these carbonyl compounds were used as terminating reagents. This enables the facile and versatile synthesis of stereoregular telechelic poly­(phenylacetylene)­s with various functional groups at both the initial and terminal chain ends because the components of aryl boronic acid derivatives used as initiators in our multicomponent catalytic system are quantitatively introduced to the initiating end of the resulting polymer.

Ar hodium-based multicomponent catalytic system for well-controlled living polymerization of phenylacetylenes has been developed. The catalytic system is composed of readily available and bench-stable [Rh(nbd)Cl] 2 ,aryl boronic acid derivatives,d iphenylacetylene,5 0% aqueous KOH, and PPh 3 .T his system offers am ethod for the facile and versatile synthesis of various end-functionalized cis-stereoregular poly-(phenylacetylene)s because components from aryl boronic acids and diphenylacetylene were introduced to the initiating end of the polymers.T he polymerization reaction shows atypical living nature with ahigh initiation efficiency,and the molecular weight of the resulting poly(phenylacetylene)s can be readily controlled with very narrowm olecular-weight distributions (M w /M n = 1.02-1.09). The experimental results suggest that the present catalytic system has ahigher polymerization activity than the polymerization activities of other rhodium-based catalytic systems previously reported.

Well-controlled living polymerization of water-soluble phenylacetylene derivatives in water was achieved for the first time using a multicomponent catalytic system consisting of [Rh(nbd)Cl] 2 , an aryl boronic acid, diphenylacetylene having carboxy groups, a tetraalkylammonium hydroxide, and a water-soluble triphenylphosphine. This catalytic system enables a direct synthesis of various water-soluble cis-stereoregular poly(phenylacetylene)s having a narrow molecular weight distribution, the molecular weight of which can be controlled by the initial feed ratio of the monomer to the catalyst. Moreover, the syntheses of water-soluble telechelic poly(phenylacetylene)s having various functional groups at both chain ends as well as a watersoluble block copolymer were achieved.

Polymerisation In ihrem Forschungsartikel (e202202676) berichten Tsuyoshi Taniguchi, Katsuhiro Maeda et al. über die Synthese von wasserlöslichen stereoregulären telechelen Poly(phenylacetylenen) durch lebende Polymerisation in Wasser.