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Synthesis of Syndiotactic Macrocyclic Poly(methyl methacrylate) via Transformation of the Growing Terminal in Stereospecific Anionic Polymerization
Author(s) -
Usuki Naoya,
Satoh Kotaro,
Kamigaito Masami
Publication year - 2017
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.201700041
Subject(s) - polymer chemistry , living anionic polymerization , polymerization , chemistry , alkyne , stereospecificity , anionic addition polymerization , methyl methacrylate , tetrahydrofuran , end group , organic chemistry , catalysis , polymer , solvent
In this study, the synthesis of well‐defined cyclic syndiotactic poly(methyl methacrylate) ( st ‐PMMA) is investigated by transformation of the growing terminal in stereospecific anionic polymerization. st ‐PMMA is first synthesized by living syndiospecific anionic polymerization in tetrahydrofuran at a low temperature, which is started with a protected‐alkyne initiator prepared in situ by metal‐halogen exchange reaction of an α‐haloester bearing a pendent protected‐alkyne with 1,1‐diphenylhexyl lithium. The anionic polymerization is terminated with halogenation of the growing enolate terminal by CBrCl 3 . The terminal halogen of the obtained st ‐PMMA is further converted into azide group, which is subsequently employed in the intramolecular copper‐catalyzed click reaction in high dilution with the alkyne‐initiating terminal after deprotection. The macrocyclic st ‐PMMA is confirmed by 1 H NMR, size exclusion chromatography, and MALDI‐TOF MS analyses.