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Zirconocenes as Photoinitiators for Free‐Radical Polymerisation of Acrylates
Author(s) -
Polo Eleonora,
Barbieri Andrea,
Sostero Silvana,
Green Malcolm L. H.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20022)2002:2<405::aid-ejic405>3.0.co;2-g
Subject(s) - chemistry , electron paramagnetic resonance , radical , steric effects , acrylate , polymerization , photochemistry , photopolymer , zirconium , polymer chemistry , radical polymerization , reagent , polymer , monomer , organic chemistry , physics , nuclear magnetic resonance
This paper reports the photochemical behaviour of unbridged ( 1−6 ) and bridged zirconocenes ( 7r , 7m ), whose substituents differ in both electron‐donor and steric properties. The study of the electronic spectra and EPR spin‐trapping experiments showed the photogeneration of ligand‐ and zirconium‐centred radicals at wavelengths higher than 350 nm. This feature makes these complexes suitable as photoinitiators for radical polymerisation processes. tert ‐Butyl acrylate polymerisation has been studied in detail and the results are particularly encouraging as far as the reaction yields and the stereochemistry are concerned. In particular, the complexes 4 − 6 , due to the tuneability of their structure and their stability in solution, look the most promising reagents.