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Synthesis of Hydroxyl‐Terminated Poly(vinylcarbazole‐ ran ‐styrene) Copolymers by Nitroxide‐Mediated Polymerization
Author(s) -
Morton Kaylyn,
Graffe Andres,
Marić Milan
Publication year - 2007
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.200600560
Subject(s) - copolymer , nitroxide mediated radical polymerization , polymer chemistry , styrene , polymerization , chemistry , radical polymerization , molar mass distribution , organic chemistry , polymer
A series of poly(vinylcarbazole‐ ran ‐styrene) copolymers with terminal hydroxyl groups were synthesized using nitroxide mediated polymerization (NMP) with the hydroxyl‐functional initiator VA‐086 and TEMPO as the mediator at 130 °C. Polymerizations were studied as a function of vinylcarbazole feed content, target molecular weight, and VA‐086/TEMPO ratio. The characterization of the copolymers was done by GPC and NMR. For feed concentrations of 40 mol‐% vinylcarbazole, copolymers with vinylcarbazole concentration up to 33 mol‐% could be obtained with narrow molecular weight distributions (PDI = 1.35) and exhibit pseudo‐“living” character up to conversions of about 20% if the target molecular weight was >100 kg · mol −1 . 1 H NMR indicated that the hydroxyl group was retained sufficiently with a functionality typically of about 0.7 hydroxyl groups per chain. Copolymers synthesized with higher vinylcarbazole feed content exhibited slower kinetics and were less controlled, resulting in much broader molecular weight distributions. The absence of control could be attributed to the absence of thermal initiation by vinylcarbazole which is advantageous toward controlling the radical concentration during the polymerization.