Post-functionalization of disubstituted polyacetylenes via click chemistry

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We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes(PAs,P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants.The precursor PA(P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains(P1).P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane(M) under the promotion of WCl6-Ph4Sn catalyst.Two synthetic routes,i.e.two-steps(from P1 to P3 via precursor P2) and one-pot(from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2.By using the techniques such as GPC,FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized. We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1) .P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WCl6-Ph4Sn catalyst.Two synthetic routes, ietwo-steps from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2.By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.
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