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Complex Brush‐Like Macromolecular Architectures via Anionic and Ring Opening Metathesis Polymerization: Synthesis, Characterization, and Thermal Properties
Author(s) -
Theodosopoulos George V.,
Bitsi SpyridoulaLida,
Pitsikalis Marinos
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.201700253
Subject(s) - romp , polymer chemistry , macromonomer , ring opening polymerization , metathesis , polymerization , anionic addition polymerization , ethylene oxide , ring opening metathesis polymerisation , chemistry , norbornene , differential scanning calorimetry , materials science , polymer , copolymer , organic chemistry , physics , thermodynamics
Abstract Combination of anionic and ring opening metathesis (ROMP) polymerizations is conducted for the synthesis of different series of brush polymers adopting the macromonomer methodology. Specifically, poly( tert ‐butoxystyrene) (P t BOS), polystyrene (PS), and poly(ethylene oxide) (PEO) macromonomers, having end norbornene groups, are prepared by anionic polymerization techniques and suitable termination reactions or functional anionic initiators. These macromonomers are either homopolymerized or copolymerized by ROMP employing Ruthenium Grubbs catalysts of the 1st or 3rd generation leading to the formation of polymer brushes. Using this synthetic approach, P t BOS polymacromonomers, P t BOS‐PEO block and random copolymacromonomers, and P t BOS‐PS random copolymacromonomers are prepared. Acidic hydrolysis of the tert ‐butoxy groups of the P t BOS brushes affords the corresponding polyhydroxystyrene (PSOH) brushes. Subsequent activation of the hydroxyl groups upon reaction with triphenylmethyl potassium and addition of ethylene oxide lead to the formation of PEO brushes on the PSOH brushes (brush on brush structures). These materials are thoroughly characterized by size exclusion chromatography, and 1 H‐NMR spectroscopy. The thermal properties are studied by differential scanning calorimetry, thermogravimetric analysis , and differential thermogravimetry.