Energy polymerizable compositions containing organometallic initiators

Claim 2

An energy polymerizable composition comprising a cationically polymerizable material and a catalytically effective amount of an ionic salt of an organometallic complex cation capable of adding an intermediate strength nucleophile or.upon photolysis capable of liberating at least one coordination site, said metal in said organometallic complex cation being selected from elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB.

Claim 3

The composition according to Claim 1 wherein said ionic salt has a formula selected from Formulas I, II, and III: wherein M a , M b , M C , and M d each represents a metal selected from the elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB; with the proviso that Formula I can represent a. mononuclear, binuclear, trinuclear, or tetranuclear complex compound comprising M a , M a M b , M a M b M c , or M a M b M c M d respectively with their attendent ligands, L; L 1a , L lb, L lc , and L ld each represents none, 1, 2, or 3 ligands contributing x-electrons that can be the same or different ligands selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve π-electrons to the valence shell of M a , M b , M c , and M d respectively; L 2a , L 2b, L 2c and L 2d each represents none or 1 to 6 ligands contributing an even number of σ-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 σ-electrons to the valence shell of M a , M b , M C , and M d respectively; L 3a, L3b, L 3c, and L 3d each represents none, 1 or 2 ligands contributing one σ-electron each to the valence shell of M a, M b , M C , and M d respectively; L 4 represents none or 1 to 6 bridging ligands containing x-electrons that can be the same or different ligand selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of acting as a bridging ligand contributing 2 to 24 π-electrons to the valence shells of two or more metal atoms M a , M b , M c , or M d simultaneously; L 5 represents none or 1 to i2 bridging-ligands contributing an even number of α-electrons that can be the same or different selected from mono, di, and tri-dentate ligands, each donating 2, 4, or 6 σ-electrons to the valence shells of two or more metal atoms M a , M b , M c, or M d simultaneously; L 6 represents none or 1 to 12 bridging ligands contributing 1, 2, 3, or 4 σ-electrons to the valence shells of two or more metal atoms M a , M b , M c , or M d simultaneously; with the proviso that the total electronic charge contributed to M a , M b , M C , and M d by the ligands L la, L 2a, L 3a, L lb, L2b , L3b , L lc, L 2c, L 3c, L ld, L 2d, L 3d, L 4, L 5 , and L 6 plus the sum of ionic charge on M a , M b , M c , and M d results in a residual net positive charge of e to the complex; e is an integer having a value of 1, 2, or 3, the residual electrical charge of the complex cation; X is a halogen containing complex anion of a metal or metalloid; f is an integer of 1 to 3, the number of complex anions required to neutralize the charge e on the complex cation, and g, h, j, and k independently are 0 or 1, with at least one of them being equal to 1; wherein M m represents a metal selected from elements of the .Periodic Groups IVB, VB, VIB, VIIB, and VIIIB; L 7 represents none, one, or two π-electron contributing ligands that can be the same or different ligand selected from substituted and unsubstituted acyclic and alicyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic and heterocyclic aromatic compounds, each capable of contributing two to twelve π-electrons to the valence shell of M m ; L 8 represents none or 1 to 6 ligands that can be the same or different ligand selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 a-electrons to the valence shell of M m ; with the proviso that the total electronic charge contributed to M m by L 7 and L 8 plus the ionic charge on M m results in a residual net positive charge of e to the complex; and e, X and f are as defined above; and wherein MP represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co; L 9 represents one or two π-electron contributing ligands that can be the same or different ligand selected from substituted and unsubstituted n 3- allyl, η 5 -cyclopentadienyl, and η 7 -cycloheptatrienyl and η 6 -aromatic compounds selected from n 6- benzene and substituted η 6 -benzene compounds and compounds having 2 to 4 fused rings each capable of contributing 3 to 12 -electrons to the valence shell of M p ; L 1 0 represents none, 1 to 3 ligands contributing two a-electrons to the valence shell of M p ; with the proviso that the total electronic charge contributed to MP by ligands L 9 and L 10 , plus the ionic charge on MP results in a residual net positive charge of q to the complex; q is an integer having a value of 1 or 2, the residual electrical charge of the complex cation; Y is a halogen containing complex anion selected from AsF 6 -, SbF 6 -, and SbF 5 OH-, and n is an integer of 1 or 2, the number of complex anions required to neutralize the charge q on the complex cation.

Claim 4

The composition according to claim 2 wherein in Formula I, the ligands L la , L l b, L lc , and L 1d of the ionic salt each contains less than.100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; the ligands L 2a , L 2b , L 2c , and L 2d of the ionic salt each is selected from: a. monodentate ligands having up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, and b. polydentate ligands capable of forming with metal M a, M b, M c , or M d a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, in addition to the metal atom; the ligands L 3a , L 3b , L 3c , and L 3d of the ionic salt each has up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; the bridging ligand L 4 of the ionic salt contains less than 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen and nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; the bridging ligand L 5 of the ionic salt contains up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, and boron; and the bridging radical L 6 of the ionic salt has up to 30 carbon atoms and up to.10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; wherein, in formula II ligand L 7 of the ionic salt contains less than 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; ligand L 8 of the ionic salt is selected from: a. monodentate ligands having up to 30 carbon atoms and up to 2 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, and b. polydentate ligands capable of forming with metal M m a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron in addition to the metal atom; and wherein, in Formula III ligand L 10 of the ionic salt is selected from carbon monoxide and the nitrosonium.ion, and ligand L 9 of the ionic salt contains up to 24 carbon and up to two heteroatoms selected form nitrogen, oxygen, and sulfur. 4. The composition according to claims 2 and 3 wherein the ligands L l a, L l b, L lc , and L ld each is independently unsubstituted or substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycarbonyl, hydrocarbylcarbonyl, hydrocarbylcarbonamido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, and wherein the ligand L 7 or L 9 is substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycarbonyl, hydrocarbylcarbonyl, hydrocarbylcarbonamido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

Claim 5

The composition according to any preceding claim wherein said polymerizable material is selected from an epoxy group containing material, 1,2- 1,3-, and 1,4-cyclic ethers (also designated as 1,2-, 1,3-, and 1,4-epoxides), vinyl ethers, N-vinyl compounds, ethylenically-unsaturated hydrocarbons, cyclic formals, and cyclic organosiloxanes.

Claim 6

The composition according to any preceding claim wherein said salt is present in an amount in the range of 0.01 to 20 weight percent of said cationically polymerizable material.

Claim 7

The composition according to any preceding claim further comprising in the range of 0.01 to 10 parts by weight of a spectral sensitizer per part of organometallic salt.

Claim 8

The composition according to claims 2 to 7 wherein said L la , L l b, L I C, L ld, L 2a, L 2b, L 2c, L 2d, L 3a, L 3b, L 3c, L 3 d, L 4 , L 5 , and L 6 ligands independently are groups on a polymeric chain.

Claim 9

A process for polymerizing the composition according to any preceding claim, said process comprising: a. admixing said cationically polymerizable material with a catalytically effective amount of said ionic salt of an organometallic complex, and b. curing the resulting admixture with a thermal or actinic radiation source.

Claim 10

A compound according to Claims 2 to 7 having the formula: wherein MP represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co; L 9 represents 1 or 2 ligands contributing w-electrons that can be the same or different ligand selected from substituted and unsubstituted n 3- allyl, η 5 -cyclopentadienyl, and n 7- cycloheptatrienyl and substituted n 6- aromatic compounds selected from η 6 -benzene and substituted η 6 -benzene compounds and compounds having 2 to 4 fused rings each capable of contributing 3 to 12 π-electrons to the valence shell of M p ; L 10 represents none or 1 to 3 ligands contributing an even number of σ-electrons that can be the same or different ligand selected from carbon monoxide or nitrosonium; with the proviso that the total electronic charge contributed to MP by L 9 and L 10 plus the ionic charge on metal M p results in a net residual positive charge of q to the complex; and q is an integer having a value of 1 or 2, the residual electrical charge of the complex cation; Y is a halogen-containing complex anion selected from AsF 6 -, SbF 6 - and SbF 5 OH-; and n is an integer having a value of 1 or 2, the number of complex anions required to neutralize the charge q on the complex cation.