Journal
POLYMER CHEMISTRY
Volume 6, Issue 26, Pages 4784-4793Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5py00657k
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Funding
- National Natural Science Foundation of China [21104015, 21172050, 21371043, 51303044, 21304027]
- Thousand Young Talents Program
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The development of novel synthetic methods for the facile preparation of well-defined stereoregular helical polyisocyanides and their block copolymers in a living/controlled fashion is of great interest. In this contribution, a family of air-stable alkylethynyl Pd(II) complexes was unexpectedly found to promote the living polymerization of phenyl isocyanide, affording poly(phenyl isocyanide)s with controlled molecular weights, narrow molecular weight distributions and high stereoregularity. Interestingly, such alkylethynyl Pd(II) complexes exhibit very high helix-sense-selectivity in the living polymerization of an optically active phenyl isocyanide bearing an L-alanine pendant with a long decyl chain, and a single handed helical poly( phenyl isocyanide) with controlled helical sense was selectively produced. Moreover, a Pd(II) complex bearing a hydroxyl group can initiate the living polymerization of both phenyl isocyanide and L-lactide in one-pot, leading to the formation of well-defined poly(phenyl isocyanide)-b-poly(L-lactic acid) copolymers in high yields with controlled molecular weights and tunable compositions. Although the two monomers were polymerized via distinct mechanisms, the block copolymerization was revealed to proceed under living/controlled manners.
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