ABSTRACT
Improved 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 Ph4 Sn and ArSnn Bu3 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 Ph4 Sn 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 -Ph4 Sn and TaCl5 -n Bu4 Sn systems.
ABSTRACT
An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long-accepted metathesis mechanism.
