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US 5,514,728 AGranted
Catalysts and initiators for polymerization
AssigneeMinnesota Mining and Manufacturing Company
InventorsWilliam M. Lamanna, Michael C. Palazzotto, Robert J. DeVoe, Fred B. McCormick, Jeffrey M. Olofson, Allen R. Siedle, Peggy S. Willett
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Abstract
Salts having a cationic portion of either a mono-, polyvent metal center, onium salts or organometallic salts and a nonnucleophilic anion are useful as catalysts and initiators that may be photochemically or thermally-activated, and polymerizable compositions containing such catalysts and initiator salts and at least one of a cationic or free-radical addition polymerizable monomers, or catalyzed step-growth polymerizable monomers.
Claims15
A polymerizable composition comprising:
- (a) at least one of a cationic addition polymerizable monomer;
- a free-radically polymerizable ethylenically-unsaturated monomer;
- a catalyzed step-growth monomer;
- or mixtures thereof and,
- (b) at least one of the salts of nonnucleophilic anions wherein the cationic portion of the salt is selected from the group consisting of:
- (1) mono- or polyvalent metal cations having a valence of 1-5 selected from the group consisting of metals of Groups IA and IIA and those of the lanthanide and actinide serires of the Periodic Table of Elements (CAS version);
- (2) organic onium cations selected from the group consisting of aliphatic or aromatic Group IVA-VIIA (CAS version) centered onium salts, and protonated aliphatic, aromatic or heterocyclic amines;
- or
- (3) organometallic complex cations essentially free of metal hydride or metal alkyl functionality and has the formula:
- (L.sup.1)(L.sup.2)M!.sup.+q
- wherein
- M represents a metal selected from the group consisting of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Pd, Pt and Ni;
- L.sup.1 represents 1 or 2 cyclic, polyunsaturated ligands that can be the same or different ligands selected from the group consisting of substituted and unsubstituted cyclopentadienyl, cyclohexyldienyl, and cycloheptatrienyl, cyclohetatriene, cyclooctatetraene, heterocyclic compounds and aromatic compounds selected from substituted and unsubstituted benzene compounds and compounds having 2 to 4 fused rings, each capable of contributing 3 to 8 electrons to the valence shell of M;
- L.sup.2 represents none, or 1 to 3 nonanionic ligands contributing an even number of electrons that can be the same or different ligands selected from the group of carbon monoxide, ketones, olefins, ethers, nitrosonium, phosphines, phosphites, and related derivatives of arsenic and antimony organonitriles, amines, alkynes, isonitriles, dinitrogen, with the proviso that the total electronic charge contributed to M results in a net residual positive charge of q to the complex;
- q is an integer having a value of 1 or 2, the residual charge of the complex cation;
- the anionic portion of the salts has the formula:
- (M').sup.m+ Q.sub.1 Q.sub.2 . . . Q.sub.n !.sup.d-
- wherein:
- M' is a metal or metalloid selected from the groups subtended by Groups IVB to VB of the Periodic Table of the Elements (CAS version);
- Q.sub.1 to Q.sub.n are selected, each independently from the group consisting of halide radicales, dialkylamido radicals, hydroxide, alkoxide and aryloxide radicals, hydrocarbylmercaptide and -carboxylate radicals, hydrocarbyl and substituted hydrocarbyl radicals, and organometalloid radicals, where at least one of Q.sub.1 to Q.sub.n is a nalogen-substituted aromatic hydrocarbyl radical, but not more than (n-1) of Q.sub.1 to Q.sub.n may be halide radical, with the remaining Q.sub.1 to Q.sub.n being selected from the foregoing radicals;
- m is an integer from 1 to 6;
- n is an integer from 2 to 7;
- and (n-m)=d.
20 more elements
Dependencies are inferred from the claim text.