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Anionic Polymerization of Reactive 3‐Chloropropyl Isocyanate
Author(s) -
Chae ChangGeun,
Shah Priyank N.,
Min Joonkeun,
Yu YongGuen,
Lee JaeSuk
Publication year - 2015
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.201400014
Subject(s) - isocyanate , polymerization , polymer chemistry , chemistry , polystyrene , sodium tetraphenylborate , yield (engineering) , polymer , steric effects , materials science , polyurethane , organic chemistry , ion , metallurgy
Summary For the synthesis of a new functional polyisocyanate, the anionic polymerization of 3‐chloropropyl isocyanate (3CPIC) was carried out using several initiator systems in THF at −98 °C. When a sodium benzanilide (Na‐BA) cluster was used as an aggregated initiator, the initiation efficiency and polymer yield were low due to too fast propagation and cyclic trimerization compared to the initiation. A more reactive oligo( n ‐hexyl isocyanate)sodium/Na‐BA cluster improved the initiation efficiency and polymer yield, but trimerization still occurred. A nearly quantitative yield was achieved by oligo(2‐vinylpyridinyl)potassium in the presence of a large excess of sodium tetraphenylborate (NaBPh 4 ). In this case, highly dissociating and bulky NaBPh 4 reduced the propagation rate and protected the propagating chain end from trimerization through steric hindrance. This advantage of NaBPh 4 was cancelled by the decreased initiation efficiency. All polymerization trials resulted in uncontrolled molecular weight properties. The chloropropyl side groups of the obtained P3CPIC reacted with polystyryllithium to generate poly(3‐chloropropyl isocyanate)‐ graft ‐polystyrene (P3CPIC‐ g ‐PS) through the grafting‐onto method.