Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis

Abstract

AbstractImproved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s by polymerization of the corresponding diphenylacetylenes using MoCl5‐ and WCl4‐based catalytic systems have been developed. MoCl5 induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph4Sn and ArSnnBu3 to produce cis‐stereoregular linear poly(diphenylacetyelene)s with high molecular weights (number‐average molar mass (Mn)=30,000–3,200,000) in good yields (up to 98 %). On the other hand, WCl4 induces ring expansion polymerization of diphenylacetylenes in the presence of Ph4Sn or reducing reagents to produce cis‐stereoregular cyclic poly(diphenylacetylene)s with high molecular weights (Mn=20,000–250,000) in moderate to good yields (up to 90 %). Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods using WCl6‐Ph4Sn and TaCl5‐nBu4Sn systems.