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High‐Molecular‐Weight Polyketones from Higher α ‐Olefins: A General Method
Author(s) -
PérezFoullerat David,
Meier Uwe W.,
Hild Sabine,
Rieger Bernhard
Publication year - 2004
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.200400273
Subject(s) - olefin fiber , polymer chemistry , polymerization , copolymer , polymer , catalysis , monomer , carbon monoxide , solvent , chemistry , glass transition , chain propagation , organic chemistry
Summary: A method to optimize the polymerization conditions in order to favor chain propagation is described for the synthesis of polymers containing low reactive, long, linear 1‐olefins and carbon monoxide (CO). It consists of the use of the olefin monomer as the polymerization solvent, together with the emulsification of a carefully chosen immiscible activator. This is given as a general method applicable to different families of catalyst able to produce 1,4‐polyketones. When the catalyst precursor is [dpppPd(NCCH 3 ) 2 ](BF 4 ) 2 , which has been extensively studied, the polymerization degrees are the highest published (up to 2.4 × 10 5 g · mol −1 ). The influence of parameters like temperature, CO pressure, volume of activator, and catalyst counter ion or ligand substitutions are reported. Some chemical and physical properties of the polymers, such as glass transition temperature, melting processes, and mechanical behavior, are examined and compared with the linear 1‐olefin homologues from C3 to C10. These properties are shown in some cases to be unprecedented.DSC profiles from the 1st scan for α ‐olefin/CO copolymers.