Catalyst for condensation of hydrolyzable silanes and storage stable compositions thereof

• US 4,101,513 A
• Filed: 02/02/1977
• Issued: 07/18/1978
• Est. Priority Date: 02/02/1977
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Fox, Frederick J., Krankkala, George E., Noren, Richard W.
• Primary Examiner(s): Jacobs, Lewis T.
• Application Number:
  US05/764,817
• Time in Patent Office: 531 Days
• Field of Search: 260/46.5 R, 260/46.5 G, 260/46.5 E, 260/46.5 UA, 260/46.5 Y, 260/77.5 A, 204/159.13
• US Class Current: 522/31
• CPC Class Codes: C08G 77/08 characterised by the catalysts used

Abstract

Onium catalysts of Group Va, VIa, and VIIa atoms have been found to be radiation activatable catalysts for the hydrolysis of silanes. Anhydrous compositions comprising silanes and the catalyst are storage stable.

Claims

1. An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula:

space="preserve" listing-type="equation">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 R² is an aromatic group at least as electron withdrawing as benzene,

R¹ 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 R² groups are bonded to A.

2. 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.

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

4. 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.

5. The polymerizable composition of claim 3 wherein the silane is represented by the formulae:

##STR14## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

6. The polymerizable composition of claim 3 wherein the silane is represented by the formula ##STR15## wherein R⁹ and R¹⁰ 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.

7. 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.

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

9. 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.

10. The polymerizable composition of claim 1 wherein a is 0 and R² is a phenyl.

11. 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.

12. 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.

13. The polymerizable composition of claim 12 wherein the silane is represented by the formulae:

##STR16## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

14. The polymerizable composition of claim 12 wherein the silane is represented by the formula ##STR17## wherein R⁹ and R¹⁰ 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.

15. 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.

16. The polymerizable composition of claim 12 wherein a is 0 and R² is a phenyl.

17. 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.

18. The polymerizable composition of claim 1 wherein R² is a phenyl group, naphthyl group, thienyl group, pyranyl group, furanyl group or pyrazolyl group.

19. The polymerizable composition of claim 18 wherein R¹ is alkyl.

20. The polymerizable composition of claim 1 wherein the silane is represented by the formulae:

##STR18## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

21. The polymerizable composition of claim 20 wherein the silane is represented by the formula ##STR19## wherein R⁹ and R¹⁰ 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.

22. 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.

23. A method for the condensation of silane comprising irradiating a composition comprising:

(1) a hydrolyzable silane,

(2) a catalytic amount of H₂ O, and

(3) an onium catalyst comprising a) a diaromatic, triaromatic, or tetraaromatic organic adduct of an organoatomic cation of a Group Va, VIa, or VIIa atom, and b) an anion,

said onium catalyst being represented by the formula;

##STR20## wherein R² is an aromatic group at least as electron withdrawing as benzene,

R¹ 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 R² groups are bonded to A

with at least a sufficient intensity of radiation to activate the onium catalyst and initiate the condensation reaction.

24. 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.

25. 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.

26. 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.

27. The method of claim 25 wherein said hydrolyzable silane is represented by the formula

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

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

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

31. The method of claim 30 wherein the polymerizable silane is represented by the formulae:

##STR21## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

32. 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.

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

34. The method of claim 33 wherein the polymerizable silane is represented by the formulae:

##STR22## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

35. The method of claim 23 wherein the polymerizable silane is represented by the formulae:

##STR23## where R⁸ 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 R⁷ 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 (CH₂ CH₂ 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.

36. The method of claim 35 wherein the polymerizable silane is represented by the formula ##STR24## wherein R⁹ and R¹⁰ 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.

37. The method of claim 23 wherein said hydrolyzable silane is represented by the formula

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

39. An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula:

space="preserve" listing-type="equation">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.

40. An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula:

space="preserve" listing-type="equation">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 R² is an aromatic group at least as electron withdrawing as benzene,

R¹ 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 R² groups are bonded to A.

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

42. 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.

43. 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.

44. An anhydrous, storage-stable, polymerizable composition comprising at least one hydrolyzable silane represented by the formula:

space="preserve" listing-type="equation">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 R² 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 R² groups are bonded to A.