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Ring‐opening polymerization of lactones using RuCl 2 (PPh 3 ) 3 as initiator: Effect of hydroxylic transfer agents
Author(s) -
MataMata José Luis,
Báez José E.,
Gutiérrez José Alfredo,
MartínezRicha Antonio
Publication year - 2005
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.22963
Subject(s) - alkoxide , chemistry , polymerization , ruthenium , polymer chemistry , ring opening polymerization , benzyl alcohol , polymer , organic chemistry , catalysis
ε‐Caprolactone and δ‐valerolactone were polymerized in bulk at 150°C using the ruthenium(II) complex RuCl 2 (PPh 3 ) 3 as initiator in the presence of 1,3‐propanediol (PD) with a series of alcohols as coinitiators. Polymerization of lactones proceeds via ruthenium(II) alkoxide active centers. 1 H‐NMR analysis revealed that the ruthenium complex reacted with the alcohol, generating in situ a ruthenium alkoxide. This species became a more active initiator of ring‐opening polymerization than was RuCl 2 (PPh 3 ) 3 . The obtained polylactones were characterized by 1 H‐ and 13 C‐NMR and matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF). The results showed the formation had occurred of α,ω‐telechelic PCL and PVL diols, in which PD had been incorporated into the polymer backbone. Depending on the nature of the alcohol used as coinitiator, PCLs with different end groups could be synthesized. Insertion of an alcohol as an end group (benzyl alcohol, n ‐octanol, or isopropanol) or into the polymeric backbone (propanediol) provided support for the conclusion that a classical coordination–insertion mechanism was operating during lactone polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006