Cyclopropenimine superbases: Competitive initiation processes in lactide polymerization

Stukenbroeker, Tyler S.; Bandar, Jeffrey S.; Zhang, Xiangyi; Lambert, Tristan H.; Waymouth, Robert M.

doi:10.1021/acsmacrolett.5b00421

Cyclopropenimine superbases: Competitive initiation processes in lactide polymerization

Journal Article · Thu Jul 30 00:00:00 EDT 2015 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.5b00421· OSTI ID:1345046

Stukenbroeker, Tyler S. ^[1]; Bandar, Jeffrey S. ^[2]; Zhang, Xiangyi ^[3]; Lambert, Tristan H. ^[2]; Waymouth, Robert M. ^[3]

Stanford Univ., Stanford, CA (United States); Office of Scientific and Technical Information (OSTI)
Columbia Univ., New York, NY (United States)
Stanford Univ., Stanford, CA (United States)

Cyclopropenimine superbases were employed in this study to catalyze the ring-opening polymerization of lactide. Polymerization occurred readily in the presence and absence of alcohol initiators. Polymerizations in the absence of alcohol initiators revealed a competitive initiation mechanism involving deprotonation of lactide by the cyclopropenimine to generate an enolate. NMR and MALDI-TOF analysis of the poly(lactides) generated from cyclopropenimines in the absence of alcohol initiators showed acylated lactide and hydroxyl end groups. Finally, model studies and comparative experiments with guanidine and phosphazene catalysts revealed the subtle influence of the nature of the superbase on competitive initiation processes.

View Accepted Manuscript (DOE)

Research Organization:: Stanford Univ., Stanford, CA (United States); Columbia Univ., New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1345046

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 8 Vol. 4; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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