Energy polymerizable polyurethane precursors

Claim 2

An energy polymerizable composition comprising polyurethane precursors and a catalytically effective amount of an ionic salt of an organometallic complex cation, the 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 polyurethane precursor is at least one polyisocyanate and at least one polyol or other isocyanate-reactive group bearing at least two isocyanate-reactive groups.

Claim 4

The composition according to claim 1 wherein said ionic salt has the formula: [((L.sup.1)(L.sup.2)M).sub.b (L.sup.3)(L.sup.4)].sup.+e X.sub.f I wherein M represents the same or different metal selected from the elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB; with the proviso that Formula I can represent a mononuclear or binuclear complex compound; L 1 represents none, 1, 2, or 3 ligands contributing pi-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 contributing two to twelve pi-electrons to the valence shell of M; L 2 represent none or 1 to 6 ligands contributing an even number of sigma-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 sigma-electrons to the valence shell of M; L 3 represents none, 1 or 2 bridging ligands having pi-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 pi-electrons to the valence shells of two metal atoms simultaneously; L 4 represents none, 1, 2 or 3 bridging ligands contributing an even number of sigma-electrons that can be the same or different selected from mono, di, and tri-dentate ligands, each donating 2, 4, or 6 sigma-electrons to the valence shells of two M simultaneously; with the proviso that the total electronic charge contributed to M by the ligands L 1 , L 2 , L 3 and L 4 plus the product of ionic charge on M with b results in a residual net positive charge of e to the complex; b is an integer having a value of 1 or 2; e is an integer having a value of 1 or 2, the residual electrical charge of the complex cation; X is an anion selected from organic sulfonate anions and halogen-containing complex anions of a metal or metalliod; f is an integer of 1 or 2, the number of anions required to neutralize the charge e on the complex cation.

Claim 5

The composition according to claim 3 wherein the ligand L 1 is provided by a monomeric or polymeric compound having an accessible unsaturated group, and contains less than 100 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, ligand L 2 is selected from: a. monodentate ligands having up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, and b. polydentate ligands capable of forming with metal M a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, in addition to the metal atom; the ligand L 3 of the ionic salt each is provided by a monomeric or polymeric compound, has an accessible unsaturated group and has up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron; the bridging ligand L 4 of the ionic salt is provided by monodentate and polydentate compound which contains less than 100 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, nitrogen, phosphorus, arsenic, selenium, antimony and tellurium.

Claim 6

The composition according to claim 4 wherein the ligand L 1 is substituted by a group selected from the group consisting of hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbylcarbonyloxy, hydrocarbylcarbonyl, hydrocarbylcarbonamido, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, diphenylarsino, diphenylstibine, tributyltin, methylseleno, ethyltelluro, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

Claim 7

The composition according to claim 1 which is at least one of radiation and thermally sensitive.

Claim 8

The composition according to claim 1 wherein said ionic salt has the formula: [(L.sup.5)(L.sup.6)M].sup.+e X.sub.f II wherein M represents a metal selected from the group consisting of elements of the Periodic Groups IVB, VB, VIB, VIIB, and VIIIB; L 5 represents none, one, or two pi-electron contributing ligands that can be the same or different ligand selected from the same groups of ligands as L 1 of formula I; L 6 represents none or 1 to 6 ligands that can be the same or different ligand, contributing an even number of sigma-electrons selected from the same groups of ligands as L 2 of formula I; with the proviso that the total electronic charge contributed to M by L 5 and L 6 plus the ionic charge on M results in a residual net positive charge of e to the complex; and e, f, and X have the same definition as defined in claim 3.

Claim 9

The composition according to claim 5 wherein ligand L 5 of the ionic salt contains less than 100 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellunium, silicon, germanium, tin, and boron; ligand L 6 of the ionic salt is selected from: a. monodentate ligands having up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, and tellurium, and b. polydentate ligands capable of forming with metal M a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 30 carbon atoms and up to 10 hetero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, and tellurium.

Claim 10

The composition according to claim 8 wherein ligand L 5 is substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycaroonyl, hydrocarbylcarbonyl, hydrocarbylcarbonimido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino. diphenylarsino, diphenylstibine, tributyltin, methylseleno, ethylselluro, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon toms and up to 10 netero atoms selected from the group consisting of nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

Claim 11

The composition according to claim 7 which is at least one of radiation and thermally sensitive.

Claim 12

The composition according to claim 1, wherein said salt is present in an amount sufficient to effect polymerization.

Claim 13

The composition according to claim 11 wherein said salt is present in an amount in the range of 0.01 to 20 weight percent of said polymerizable composition.

Claim 14

The composition according to claim 11 wherein said salt is present in an amount in the range of 0.1 to 5.0 weight percent of said polymerizable composition.

Claim 15

The composition according to claim 11 wherein said salt is present in an amount in the range of 0.5 to 2.0 weight percent of said polymerizable composition.

Claim 16

The composition according to claim 6 which has been subjected to sufficient energy to effect polymerization and provide a cured composition.

Claim 17

The composition according to claim 1 wherein said di- or polyisocyanate is an aliphatic, cycloaliphatic, araliphatic, aromatic, or heterocyclic polyisocyanate, or any combination thereof.

Claim 18

The composition according to claim 16 wherein said di or polyisocyanate has the formula Q(NCO)n wherein n=an integer 2 to 4 and Q=represents an aliphatic hydrocarbon radical containing from 2 to 100 carbon atoms, and zero to 50 heteroatoms, a cycloaliphatic hydrocarbon radical containing from 4 to 100 carbon atoms and zero to 50 heteroatoms, an aromatic hydrocarbon radical or heterocyclic aromatic radical containing from 6 to 15 carbon atoms and zero to 10 heteroatoms, or an araliphatic hydrocarbon radical containing from 8 to 100 carbon atoms and zero to 50 heteroatoms, wherein the heteroatoms in all of the radicals are selected from the group consisting of non-peroxidic oxygen, sulfur, non-amino nitrogen, halogen, silicon, and non-phosphine phosphorus.

Claim 19

The composition according to claim 2 wherein said isocyanate-reactive compound contains hydroxyl, thiol, amino, or carboxyl groups.

Claim 20

The composition according to claim 1 wherein said ionic salt contains iron or manganese.

Claim 21

The composition according to claim 1 further comprising in the range of 0.01 to 10 parts by weight of a photosensitizer or photoaccelerator per part of organometallic salt.

Claim 22

A process of polymerizing polyurethane precursor composition comprising the steps of: a. admixing said polyurethane precursor composition with a catalytically effective amount of an ionic salt of an organometallic complex cation, the metal in said organometallic complex being selected from the group consisting of elements of Periodic Groups IVB, VB, VIB, VIIB, VIIIB, and b. curing the resulting admixture with at least one of a thermal or actinic radiation source.

Claim 23

A process of polymerizing polyurethane precursor composition comprising the steps of: a. admixing said polyurethane precursor composition with a catalytically effective amount of an ionic salt of an organometallic complex cation, the metal in said organometallic complex being selected from the group consisting of elements of Periodic Groups IVB, VB, VIB, VIIB, VIIIB, and b. curing the resulting admixture with at least one of a thermal or actinic radiation source.

Claim 24

The process according to claim 21 wherein said curing is a two-stage process comprising the sequential steps of: a. irradiating said composition to activate said ionic salt, and b. heating the activated composition.

Claim 25

An article comprising the composition according to claim 1.

Claim 26

An article comprising the composition according to claim 21.

Claim 27

The article according to claim 24 which is a photoresist, a layered structure, a shaped article, or a foamed article.