Catalyst for condensation of hydrolyzable silanes and storage stable compositions thereof

Claim 2

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4, and an organic aromatic onium ctalyst comprising an aromatic adduct of (1) a diaromatic, triaromatic, or tetraaromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, said onium catalyst being represented by the formula: ##STR13## wherein R 2 is an aromatic group at least as electron withdrawing as benzene, R 1 is an alkyl or alkenyl group, A is a Group Va, VIa, or VIIa atom, X is an anion, n is a positive whole integer of at least 2 up to the valence of A plus one, a is 0 or a positive whole integer up to the valence of A minus one, and n plus a is equal to the valence of A plus one and wherein at least two of said R 2 groups are bonded to A.

Claim 3

The polymerizable composition of claim 1 wherein said Group Va, VIa, or VIIa atom is selected from the group consisting essentially of phosphorous, sulfur, nitrogen, iodine or antimony.

Claim 4

The polymerizable composition of claim 2 wherein the organic aromatic catalyst is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 5

the polymerizable composition of claim 3 wherein the anion is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, bis(perfluoroalkylsulfonyl)methane, iodide, bromide, chloride, fluoride, sulfate, acetate, or trichloroacetate.

Claim 6

The polymerizable composition of claim 3 wherein the silane is represented by the formulae: ##STR14## where R 8 is a non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 or 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 7

The polymerizable composition of claim 3 wherein the silane is represented by the formula ##STR15## wherein R 9 and R 10 are independently alkylene groups of up to 4 carbon atoms, R' is an alkyl group of up to 6 carbon atoms, and u is 0 or 1.

Claim 8

The polymerizable composition of claim 3 wherein the silane is selected from the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 9

The polymerizable composition of claim 1 wherein the organic aromatic catalyst is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 10

The polymerizable composition of claim 1 wherein the aninon is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, bis(perfluoroalkylsulfonyl)methane, iodide, bromide, chloride, fluoride, sulfate, acetate, or trichloroacetate.

Claim 11

The polymerizable composition of claim 1 wherein a is 0 and R 2 is a phenyl.

Claim 12

The polymerizable composition of claim 10 wherein the anion is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, bis(perfluoroalkylsulfonyl)methane, iodide, bromide, chloride, fluoride, sulfate, acetate, or trichloroacetate.

Claim 13

The polymerizable composition of claim 1 wherein said Group Va, VIa, or VIIa is selected from the group consisting essentially of phosphorus, sulfur, nitrogen, iodine or antimony, and an anion.

Claim 14

The polymerizable composition of claim 12 wherein the silane is represented by the formulae: ##STR16## where R 8 is a non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 or 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 15

The polymerizable composition of claim 12 wherein the silane is represented by the formula ##STR17## wherein R 9 and R 10 are independently alkylene groups of up to 4 carbon atoms, R' is an alkyl group of up to 6 carbon atoms, and u is 0 or 1.

Claim 16

The polymerizable composition of claim 12 wherein the silane is selected from the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 17

The polymerizable composition of claim 12 wherein a is 0 and R 2 is a phenyl.

Claim 18

The polymerizable composition of claim 16 wherein the anion is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, bis(perfluoroalkylsulfonyl)methane, iodide, bromide, chloride, fluoride, sulfate, acetate, or trichloroacetate.

Claim 19

The polymerizable composition of claim 1 wherein R 2 is a phenyl group, naphthyl group, thienyl group, pyranyl group, furanyl group or pyrazolyl group.

Claim 20

The polymerizable composition of claim 18 wherein R 1 is alkyl.

Claim 21

The polymerizable composition of claim 1 wherein the silane is represented by the formulae: ##STR18## where R 8 is a non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 or 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 22

The polymerizable composition of claim 20 wherein the silane is represented by the formula ##STR19## wherein R 9 and R 10 are independently alkylene groups of up to 4 carbon atoms, R' is an alkyl group of up to 6 carbon atoms, and u is 0 or 1.

Claim 23

The polymerizable composition of claim 1 wherein the silane is selected fom the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 26

The method of claim 23 wherein said hydrolyzable silane is selected from the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 27

A method for the condensation of silane according to claim 23 wherein said Group Va, VIa, or VIIa atom is selected from the group consisting essentially of phosphorous, sulfur, nitrogen, iodine, or antimony.

Claim 28

The method of claim 25 wherein said hydrolyzable silane is selected from the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltriemethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 29

The method of claim 25 wherein said hydrolyzable silane is represented by the formula X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4.

Claim 30

The method of claim 27 wherein m is 3 and R is acryloxy.

Claim 31

The method of claim 28 wherein the organic adduct is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 32

The method of claim 25 wherein the organic adduct is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 33

The method of claim 30 wherein the polymerizable silane is represented by the formulae: ##STR21## where R 8 is a non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 or 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 34

The method of claim 30 wherein said hydrolyzable silane is selected from the group consisting of dimethyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanotopropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Claim 35

The method of claim 23 wherein the organic adduct is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 36

The method of claim 33 wherein the polymerizable silane is represented by the formulae: ##STR22## where R 8 is a non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 to 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 37

The method of claim 23 wherein the polymerizable silane is represented by the formulae: ##STR23## where R 8 is an non-hydrolyzable divalent hydrocarbon group of less than 20 carbon atoms or a divalent group of less than 20 carbon atoms the backbone of which is composed of only C, N, S, and O atoms with no two heteroatoms adjacent within the backbone of the divalent groups, q is 0 or 1 and R 7 is an aliphatic hydrocarbon group of less than 10 carbon atoms, an acyl group of less than 10 carbon atoms, or a group of formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is an aliphatic hydrocarbon group of less than 10 carbon atoms or hydrogen.

Claim 38

The method of claim 35 wherein the polymerizable silane is represented by the formula ##STR24## wherein R 9 and R 10 are independently alkylene groups of up to 4 carbon atoms, R' is an alkyl group of up to 6 carbon atoms, and u is 0 or 1.

Claim 39

The method of claim 23 wherein said hydrolyzable silane is represented by the formula X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4.

Claim 40

the method of claim 37 wherein m is 3 and R is acryloxy.

Claim 41

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4, and an organic aromatic onium catalyst comprising an aromatic adduct of (1) an aromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, with the proviso that when the Group Va, VIa, or VIIa atom is a halogen atom, the organoatomic cation must be at least diaromatic, and wherein aromatic groups atached to said Group Va, VIa, or VIIa atoms are at least as electron withdrawing as benzene.

Claim 42

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4, and an organic aromatic onium catalyst comprising an aromatic adduct of (1) an aromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, with the proviso that when the Group Va, VIa, or VIIa atom is a halogen atom, the organoatomic cation must be at least diaromatic, and wherein aromatic groups atached to said Group Va, VIa, or VIIa atoms are at least as electron withdrawing as benzene.

Claim 43

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is an acryloxy group, and m is 3, and an organic aromatic onium catalyst comprising an aromatic adduct of (1) a diaromatic, triaromatic, or tetraaromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, said onium catalyst being represented by the formula: ##STR25## wherein R 2 is an aromatic group at least as electron withdrawing as benzene, R 1 is an alkyl or alkenyl group, A is a Group Va, VIa, or VIIa atom, X is an anion, n is a positive whole integer of at least 2 up to the valence of A plus one, a is 0 or a positive whole integer up to the valence of A minus one, and n plus a is equal to the valence of A plus one and wherein at least two of said R 2 groups are bonded to A.

Claim 44

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is an acryloxy group, and m is 3, and an organic aromatic onium catalyst comprising an aromatic adduct of (1) a diaromatic, triaromatic, or tetraaromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, said onium catalyst being represented by the formula: ##STR25## wherein R 2 is an aromatic group at least as electron withdrawing as benzene, R 1 is an alkyl or alkenyl group, A is a Group Va, VIa, or VIIa atom, X is an anion, n is a positive whole integer of at least 2 up to the valence of A plus one, a is 0 or a positive whole integer up to the valence of A minus one, and n plus a is equal to the valence of A plus one and wherein at least two of said R 2 groups are bonded to A.

Claim 45

The polymerizable composition of claim 40 wherein the organic aromatic catalyst is a diphenyl, triphenyl, or tetraphenyl organic adduct.

Claim 46

The polymerizable composition of claim 41 wherein said Group Va, VIa, or VIIa atom is selected from the group consisting of phosphorous, sulfur, nitrogen, iodine, or antimony.

Claim 47

The polymerizable composition of claim 42 wherein X is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, bis(perfluoroalkylsulfonyl)methane, iodide, bromide, chloride, fluoride, sulfate, acetate, and trichloroacetate.

Claim 48

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4, and a catalyst capable of curing the silane in the presence of water after exposure to radiation, said catalyst consisting essentially of an organic aromatic onium catalyst comprising an aromatic adduct of (1) a diaromatic, triaromatic, or tetraaromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, said onium catalyst being represented by the formula: ##STR26## wherein R 2 is an aromatic group at least as electron withdrawing as benzene, R.sup. is an alkyl or alkenyl group, A is a Group Va, VIa, or VIIa atom, X is an anion, n is a positive whole integer of at least 2 up to the valence of A plus one, a is 0 or a positive whole integer up to the valence of A minus one, and n plus a is equal to the valence of A plus one and wherein at least two of said R 2 groups are bonded to A.

Claim 49

An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula: X.sub.m SiR.sub.4-m wherein X is a hydrolyzable group or hydrogen, R is a hydrocarbyl group, and m is 2, 3, or 4, and a catalyst capable of curing the silane in the presence of water after exposure to radiation, said catalyst consisting essentially of an organic aromatic onium catalyst comprising an aromatic adduct of (1) a diaromatic, triaromatic, or tetraaromatic organoatomic cation of a Group Va, VIa, or VIIa atom and (2) an anion, said onium catalyst being represented by the formula: ##STR26## wherein R 2 is an aromatic group at least as electron withdrawing as benzene, R.sup. is an alkyl or alkenyl group, A is a Group Va, VIa, or VIIa atom, X is an anion, n is a positive whole integer of at least 2 up to the valence of A plus one, a is 0 or a positive whole integer up to the valence of A minus one, and n plus a is equal to the valence of A plus one and wherein at least two of said R 2 groups are bonded to A.