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Design of Optimized Reaction Conditions for the Efficient Living Anionic Polymerization of Cyclopropane‐1,1‐Dicarboxylates
Author(s) -
Benlahouès Antoine,
Brissault Blandine,
Boileau Sylvie,
Penelle Jacques
Publication year - 2018
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201700463
Subject(s) - cyclopropane , dispersity , polymerization , monomer , polymer chemistry , chemistry , size exclusion chromatography , living anionic polymerization , anionic addition polymerization , organic chemistry , polymer , ring (chemistry) , enzyme
A reinvestigation of the experimental parameters used when polymerizing anionically a cyclopropane‐1,1‐dicarboxylate indicates that several key steps have to be considered, but that other steps—including some routinely used up to now—although not harmful, are nevertheless useless. A robust protocol is thus designed whose implementation allows us to routinely control the polymerization of di‐ n ‐propyl cyclopropane‐1,1‐dicarboxylate, used as a model monomer for the entire family of cyclopropyl monomers geminally activated by two ester groups. Degrees of polymerization of up to 200 can be routinely obtained, with polydispersity indexes lower than 1.05. In some cases, a small shoulder can be identified in the size exclusion chromatography (SEC) chromatogram, although not systematically. The close proximity between the two distributions affects the polydispersity index only marginally ( M w / M n still in the 1.01–1.05 range), and highly resolutive SEC columns are needed in order to identify the issue. Finally, attempts to use organic superbases other than tBuP 4 have failed thus far.