Granted Patent B2

US 8,575,292 · App. 11/789,258 · Granted Nov 5, 2013

Abstract

Claims (104)

1. A hydroxyl-functional carbamoyl organosilicon compound which possesses:

(i) at least one hydroxyl group bonded to a carbon atom and at least one carbamoyl group covalently bonded to a silicon atom through a silicon-carbon bond, and

(ii) at least one divalent oxygen-containing group possessing at least two silyloxy bonds, wherein the hydroxyl-functional carbamoyl organosilicon compound is represented by the Formula (1):

wherein:

each occurrence of R 1 , R 2 and R 3 is independently a divalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms;

each occurrence of R 4 is independently hydrogen, a hydrocarbyl group, an —R 1 SiX 1 a Z b b Z c c group or a —C(═O)OR 6 (OH) f group where R 6 is independently a divalent or polyvalent hydrocarbylene group;

each occurrence of R 5 is independently hydrogen, a hydrocarbyl group or an —R 1 SiX l a Z b b Z c c group;

each occurrence of X 1 is independently —Cl, —Br, R 7 O—, R 7 C(═O)O—, R 7 2 C═NO—, R 7 2 NO—, R 7 2 N—, —R 7 , or (HO) h-1 R 8 O— wherein each R 7 is independently hydrogen or a hydrocarbyl group and each R 8 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms;

each occurrence of Z b is independently [—OR 9 (OH) i-2 O—] 0.5 wherein each occurrence of R 9 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms, and where [—OR 9 (OH) i-2 O—] 0.5 refers to one-half of a bridging dialkoxy group;

each occurrence of Z c is independently a —OR 10 (OH) j-2 O— group wherein R 10 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms; and,

subscripts a, b, c, d, e, f, g and h are integers wherein a is 0 to 2; b is 0 to 3; c is 0 or 1; d is 1 to 4; e is 0 to 20, f is 1 to 4; g is 1 to 100; h is 2 to 3; i is 2 to 3 and j is 2 to 3, provided, when c is 1, a+b is 1; and when b is 0, then g is 1 and c is 1, wherein said hydroxyl-functional carbamoyl organosilicon compound is selected from the group consisting of [3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

{3-[2-(3-hydroxy-2-methyl-propoxy)-5-methyl-[1,3,2]dioxasilinan-2-yl]-propyl}-carbamic acid 2-hydroxy-ethyl ester;

[3-(2-ethoxy-5-methyl-[1,3]dioxan-2-yl)-propyl]-[3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-{[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propylamino]-methyl}-carbamic acid 2-hydroxy-ethyl ester;

({(2-hydroxy-ethoxycarbonyl)-[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-amino}-methyl)-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

({(2,3-dihydroxy-propoxycarbonyl)-[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-amino}-methyl)-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2,3-dihydroxy-propyl ester;

[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-{[[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-(2-hydroxy-1-methyl-ethoxycarbonyl)-amino]-methyl}-carbamic acid 3-hydroxy-1-methyl-propyl ester;

[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-{[[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-(2-hydroxy-1-methyl-ethoxycarbonyl)-amino]-methyl}-carbamic acid 3-hydroxy-1-methyl-propyl ester;

[4-(2-ethoxy-4-methyl-[1,3,2]dioxasilinan-2-yl)-butyl]-[3-(2-ethoxy-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 3-hydroxy-1-hydroxymethyl-propyl ester;

{3-[2-(3-{2-[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-propyl}-carbamic acid 3-hydroxy-propyl ester;

{3-[bis-(3-{2-[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-3-hydroxypropoxy-silanyl]-propyl}-carbamic acid 3-hydroxy-propyl ester;

{3-[{3-[[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-(3-hydroxy-propoxy)-methyl-silanyloxy]-propoxy}-(3-hydroxy-propoxy)-methyl-silanyl]-propyl}-carbamic acid 2-hydroxy-ethyl ester;

{[ethyl-{3-[ethyl-[(2-hydroxy-ethoxycarbonylamino)-methyl]-(3-hydroxy-propoxy)-silanyloxy]-propoxy}-(3-hydroxy-propoxy)-silanyl]-methyl}-carbamic acid 2-hydroxy-ethyl ester;

{3-[(2-hydroxy-ethoxycarbonylamino)-methyl]-1,1,3,3-tetrahydroxy-disiloxanylmethyl}-carbamic acid 2-hydroxy-ethyl ester; and

{3-[(2-hydroxy-ethoxycarbonylamino)-methyl]-1,1,3,3-tetramethyl-disiloxanylmethyl}-carbamic acid 2-hydroxy-ethyl ester.

2. The hydroxyl-functional carbamoyl organosilicon compound claim 1 , wherein said hydroxyl-functional carbamoyl organosilicon compound is

[3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

{3-[2-(3-hydroxy-2-methyl-propoxy)-5-methyl-[1,3,2]dioxasilinan-2-yl]-propyl}-carbamic acid 2-hydroxy-ethyl ester or

[3-(2-ethoxy-5-methyl-[1,3]dioxan-2-yl)-propyl]-[3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester.

3. The hydroxyl-functional carbamoyl organosilicon compound of claim 1 which upon the substantially complete hydrolysis thereof generates from 0 to no more than 10 weight percent VOC(s).

4. The hydroxyl-functional carbamoyl organosilicon compound of claim 1 which upon the substantially complete hydrolysis thereof generates from 0 to no more than 1 weight percent HAP(s) based upon the total weight of the substantially non-hydrolyzed compound.

5. The hydroxyl-functional carbamoyl organosilicon compound of claim 1 which upon the substantially complete hydrolysis thereof generates from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) based upon the total weight of the substantially non-hydrolyzed compound.

6. A coating composition comprising an aqueous solution of at least one hydroxyl-functional carbamoyl organosilicon compound of claim 1 .

7. A coating composition comprising an aqueous solution of at least one hydroxyl-functional carbamoyl organosilicon compound of claim 2 .

8. A coating composition comprising an aqueous solution of at least one hydroxyl-functional organosilicon compound of claim 3 .

9. A coating composition comprising an aqueous solution of at least one hydroxyl-functional organosilicon compound of claim 4 .

10. A coating composition comprising an aqueous solution of at least one hydroxyl-functional organosilicon compound of claim 5 .

11. The coating composition of claim 6 further comprising at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

12. The coating composition of claim 7 further comprising at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

13. The coating composition of claim 8 further comprising at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

14. The coating composition of claim 9 further comprising at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

15. The coating composition of claim 10 further comprising at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

16. The coating composition of claim 13 wherein the total amount of additional component(s) represents from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) of the weight of the composition.

17. The coating composition of claim 13 wherein the total amount of additional component(s) represents from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) of the weight of the composition.

18. The coating composition of claim 13 wherein the total amount of additional component(s) represents from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) of the weight of the composition.

19. A method for coating at least a portion of the exposed surface of a metal which comprises:

a) applying to said surface a curable coating composition comprising an aqueous solution of at least one partially or substantially completely hydrolyzed hydroxyl-functional carbamoyl organosilicon compound which possesses:

(i) at least one hydroxyl group bonded to a carbon atom and at least one carbamoyl group covalently bonded to a silicon atom through a silicon-carbon bond, and

(ii) at least one divalent oxygen-containing group possessing at least two silyloxy bonds, wherein the hydroxyl-functional carbamoyl organosilicon compound is represented by the Formula (1):

wherein:

each occurrence of R 1 , R 2 and R 3 is independently a divalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms;

each occurrence of R 4 is independently hydrogen, a hydrocarbyl group, an —R 1 SiX 1 a Z b b Z c c group or a —C(═O)OR 6 (OH) f group where R 6 is independently a divalent or polyvalent hydrocarbylene group;

each occurrence of R 5 is independently hydrogen, a hydrocarbyl group or an —R 1 SiX 1 a Z b b Z c c group;

each occurrence of X 1 is independently —Cl, —Br, R 7 O—, R 7 C(═O)O—, R 7 2 C═NO—, R 7 2 NO—, R 7 2 N—, —R 7 , or (HO) h-1 R 8 O— wherein each R 7 is independently hydrogen or a hydrocarbyl group and each R 8 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms;

each occurrence of Z b is independently [—OR 9 (OH) i-2 O—] 0.5 wherein each occurrence of R 9 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms, and where [—OR 9 (OH) i-2 O—] 0.5 refers to one-half of a bridging dialkoxy group;

each occurrence of Z c is independently a —OR 10 (OH) j-2 O— group wherein R 10 is independently a divalent or polyvalent hydrocarbylene group, optionally containing one or more etheric oxygen atoms; and,

subscripts a, b, c, d, e, f, g and h are integers wherein a is 0 to 2; b is 0 to 3; c is 0 or 1; d is 1 to 4; e is 0 to 20, f is 1 to 4; g is 1 to 100; h is 2 to 3; i is 2 to 3 and j is 2 to 3, provided, when c is 1, a+b is 1; and when b is 0, then g is 1 and c is 1; and,

b) curing the curable coating composition on the surface of the metal to provide an anti-corrosion and/or adhesion promoting coating thereon.

20. The method of claim 19 , wherein:

each occurrence of R 1 , R 2 and R 3 is independently an alkylene, alkenylene, arenylene or aralkylene group of up to 12 carbon atoms, optionally containing one or more etheric oxygen atoms;

each occurrence of R 4 is independently hydrogen or a —C(═O)OR 6 (OH)f group;

each occurrence of R 5 is hydrogen;

each occurrence of R 6 is independently a divalent alkylene, alkenylene, arenylene, arylene or aralkylene group of up to 12 carbon atoms;

each occurrence of X 1 is independently R 7 O— or (HO) h-1 R 8 O—, wherein R 7 is an alkyl group of from 1 to 3 carbon atoms, and each R 8 is an alkylene, alkenylene, arenylene, arylene or aralkylene group of up to 15 carbon atoms, optionally containing one or more etheric oxygen atoms;

each Z b is [—OR 9 (OH) i-2 O—] 0.5 wherein R 9 is independently an alkylene, alkenylene, arenylene, arylene or aralkylene group of up to 15 carbon atoms, optionally containing one or more etheric oxygen atoms and where [—OR 9 (OH) i-2 O—] 0.5 refers to one-half of a bridging dialkoxy group;

each Z c is —OR 10 (OH) j-2 O— wherein R 10 is independently an alkylene, alkenylene, arenylene, arylene or aralkylene group of up to 15 carbon atoms, optionally containing one or more etheric oxygen atoms; and

subscripts a, b, c, d, e, f, g and h are integers wherein a is 0 to 2; b is 1 to 3; c is 0 or 1; d is 1 to 4; e is 0 to 20, f is 1 or 2; g is 2 to 8; h is 2; i is 2 and j is 2, provided, when c is 1, a+b is 1.

21. The method of claim 17 , wherein:

each occurrence of R 1 , R 2 and R 3 is independently an alkylene group of up to 12 carbon atoms;

each occurrence of R 4 is independently hydrogen or a —C(═O)OR 6 (OH) f group;

each occurrence of X 1 is independently R 7 O— or (HO) h-1 R 8 O—, wherein R 7 is an alkyl group of from 1 to 3 carbon atoms, and each R 8 is an alkylene group of up to 15 carbon atoms;

each Z b is [—OR 9 (OH) i-2 O—] 0.5 wherein R 9 is independently an alkylene group of up to 15 carbon atoms, and where —OR 9 (OH) i-2 O— refer to one-half of a bridging dialkoxy group;

each Z c is —OR 10 (OH) j-2 O— wherein R 10 is independently an alkylene group of up to 15 carbon atoms; and

subscripts a, b, c, d, e, f, g and h are integers wherein a is 0 to 1; b is 0; c is 1; d is 1 to 4; e is 0; g is 1; h is 2; i is 2 and j is 2.

22. The method of claim 20 wherein the hydroxyl-functional carbamoyl organosilicon compound includes at least one oligomer thereof.

23. The method of claim 19 wherein the hydroxyl-functional carbamoyl organosilicon compound is at least one compound selected from the group consisting of

[3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

{3-[2-(3-hydroxy-2-methyl-propoxy)-5-methyl-[1,3,2]dioxasilinan-2-yl]-propyl}-carbamic acid 2-hydroxy-ethyl ester;

[3-(2-ethoxy-5-methyl-[1,3]dioxan-2-yl)-propyl]-[3-(2-ethoxy-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-{[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propylamino]-methyl}-carbamic acid 2-hydroxy-ethyl ester;

({(2-hydroxy-ethoxycarbonyl)-[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-amino}-methyl)-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 2-hydroxy-ethyl ester;

({(2,3-dihydroxy-propoxycarbonyl)-[3-(2,4,4,6-tetramethyl-[1,3]dioxan-2-yl)-propyl]-amino}-methyl)-[3-(2,4,4,6-tetramethyl-[1,3,2]dioxasilinan-2-yl)-propyl]carbamic acid 2,3-dihydroxy-propyl ester;

[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-{[[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-(2-hydroxy-1-methyl-ethoxycarbonyl)-amino]-methyl}-carbamic acid 3-hydroxy-1-methyl-propyl ester;

[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-{[[3-(2,4-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]-(2-hydroxy-1-methyl-ethoxycarbonyl)-amino]-methyl}-carbamic acid 3-hydroxy-1-methyl-propyl ester;

[4-(2-ethoxy-4-methyl-[1,3,2]dioxasilinan-2-yl)-butyl]-[3-(2-ethoxy-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-carbamic acid 3-hydroxy-1-hydroxymethyl-propyl ester;

{3-[2-(3-{2-[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-propyl}-carbamic acid 3-hydroxy-propyl ester;

{3-[bis-(3-{2-[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-3-hydroxypropoxy-silanyl]-propyl}-carbamic acid 3-hydroxy-propyl ester;

{3-[{3-[[3-(2-hydroxy-ethoxycarbonylamino)-propyl]-(3-hydroxy-propoxy)-methyl-silanyloxy]-propoxy}-(3-hydroxy-propoxy)-methyl-silanyl]-propyl}-carbamic acid 2-hydroxy-ethyl ester;

{[ethyl-{3-[ethyl-[(2-hydroxy-ethoxycarbonylamino)-methyl]-(3-hydroxy-propoxy)-silanyloxy]-propoxy}-(3-hydroxy-propoxy)-silanyl]-methyl}-carbamic acid 2-hydroxy-ethyl ester;

{3-[(2-hydroxy-ethoxycarbonylamino)-methyl]-1,1,3,3-tetrahydroxy-disiloxanylmethyl}-carbamic acid 2-hydroxy-ethyl ester; and

{3-[(2-hydroxy-ethoxycarbonylamino)-methyl]-1,1,3,3-tetramethyl-disiloxanylmethyl}-carbamic acid 2-hydroxy-ethyl ester.

24. The method of claim 19 wherein the hydroxyl-functional carbamoyl organosilicon compound upon the substantially complete hydrolysis thereof generates from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) based upon the total weight of the substantially non-hydrolyzed compound.

25. The method of claim 20 wherein the hydroxyl-functional carbamoyl organosilicon compound upon the substantially complete hydrolysis thereof generates from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) based upon the total weight of the substantially non-hydrolyzed compound.

26. The method of claim 22 wherein the hydroxyl-functional carbamoyl organosilicon compound upon the substantially complete hydrolysis thereof generates from 0 to no more than 10 weight percent VOC(s) and from 0 to no more than 1 weight percent HAP(s) based upon the total weight of the substantially non-hydrolyzed compound.

27. The method of claim 19 wherein the coating composition further comprises at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

28. The method of claim 20 wherein the coating composition further comprises at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

29. The method of claim 22 wherein the coating composition further comprises at least one additional component selected from the group consisting of surfactant, cosolvent, pH modifier and curing catalyst.

30. The method of claim 19 wherein the metal is copper, silver, brass, titanium, titanium alloy, gold, tin, nickel, chromium, tantalum, surface cold-rolled steel, galvanized steel, hot dip galvanized steel, prime steel, aluminum, steel coated with e.g., at least one of zinc, zinc alloy, aluminum, aluminum alloy and iron.

31. The method of claim 19 wherein the cured anti-corrosion and/or adhesion promoting coating possesses a further coating thereon.

32. The method of claim 31 wherein the further coatings is a paint.

33. The coated metal article resulting from the method of claim 19 .

34. The coated metal article resulting from the method of claim 31 .

Assignments (26)