Free radical copper(II)-enolate polymerization initiators
AssigneeThe University of Akron
InventorsH. James Harwood, Stephen D. Goodrich
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Abstract
The invention describes a redox initiating system consisting of Cu.sup.II salts, enolizable aldehydes and ketones, and various combinations of coordinating agents for Cu.sup.II, coordinating agents for Cu.sup.I, and a strong amine base that is not oxidized by Cu.sup.II. In particular, Cu.sup.II octanoate/dibenzyl ketone/pyridine/triethylamine/triphenylphosphine systems are effective. In addition to initiating free radical polymerizations and copolymerizations, this initiating system can be applied to the synthesis of functionalized telechelics, polymers with ketone linkages in the backbone, block and graft copolymers consisting of free-radical and step-growth polymer blocks, and crosslinking reactions.
Claims24
A free-radical initiating redox system for polymerization comprising:
- (a) a Cu.sup.II salt soluble in the initiating system;
- (b) an initiator selected from the group consisting of formulas (I), (II) and (III) ##STR15## having at least one enolizable hydrogen atom and wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are radicals selected from the group consisting of H, alkyl, aryl, aralkyl, alkaryl, heterocycles, polycondensate polymers, polymers from free radically polymerizable monomers and other groups that do not interfere with the oxidation or initiation/polymerization reactions, and wherein the radicals can be the same or different, the Cu.sup.II converting the initiator into .alpha.-carbonyl free radicals through oxidation of the enolate form of the initiator, the radicals capable of initiating free radical polymerizations while retaining a ketone linkage;
- and
- (c) at least one monomer that can be polymerized by free-radical polymerization and that does not bear functionality that interferes with the initiation process and that further neither the monomer nor radicals derived from the monomer, nor radicals derived from the initiator are oxidized by Cu.sup.II.
Dependencies are inferred from the claim text.