期刊
ACS MACRO LETTERS
卷 4, 期 8, 页码 853-856出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsmacrolett.5b00421
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资金
- National Science Foundation [DMR-1407658, CHE-1306730]
- National Institutes of Health (NIHGMS) [R01 GM102611]
- NSF
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1306730] Funding Source: National Science Foundation
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1407658] Funding Source: National Science Foundation
Cyclopropenimine superbases were employed 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. Model studies and comparative experiments with guanidine and phosphazene catalysts revealed the subtle influence of the nature of the superbase on competitive initiation processes.
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