Curable coating compositions of silane functional polymers

• US 10,640,641 B2
• Filed: 04/19/2018
• Issued: 05/05/2020
• Est. Priority Date: 02/23/2015
• Status: Active Grant

• Current Assignee: King Industries
• Original Assignee: King Industries
• Inventors: Ravichandran, Ramanathan, Florio, John, Hsieh, Bing, Switala, David P.
• Primary Examiner(s): Pepitone, Michael F
• Application Number:
  US15/956,817
• Publication Number:
  US 20180237635A1
• Time in Patent Office: 747 Days
• CPC Class Codes: C08G 2261/76 crosslinking
• CPC Class Codes: C08K 3/28 Nitrogen-containing compounds
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/175 containing COOH-groups; Esters or salts thereof
• CPC Class Codes: C08K 5/29 Compounds containing one or more carbon-to-nitrogen double bonds
• CPC Class Codes: C08K 5/5419 containing at least one Si—C bond
• CPC Class Codes: C08K 5/544 containing nitrogen
• CPC Class Codes: C08K 5/5475 containing at least one C≡N bond
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/04 Polyamides derived from alpha-amino carboxylic acids C08L77/10 takes precedence
• CPC Class Codes: C08L 77/12 Polyester-amides
• CPC Class Codes: C09J 167/00 Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09J177/12; based on polyester-imides C09J179/08; Adhesives based on derivatives of such polymers

Abstract

There is a tin-free curable composition having (A) one or more organic polymers having a reactive-silicon-containing group, wherein at least one polymer has a main chain skeleton selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers; (B) from 0.001 to 20 parts by weight for 100 parts by weight of the organic polymer(s) (A) of a silanol condensation catalyst consisting of one or more metal amidine complexes and one or more amine carboxylate salts, (C) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an epoxysilane, an epoxysiloxane, an aminosilane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof; and (D) at least one adhesion promoter chosen from a silane or siloxane other than the compounds listed under (C). There is also a cured polymer formed from the tin-free curable composition.

Claims

1. A silanol condensation catalyst consisting of a mixture of one or more metal amidine complexes and one or more amine carboxylate salts, wherein the amidine is a guanidine, and wherein the guanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.

2. The silanol condensation catalyst of claim 1, wherein the one or more metal amidine complexes is of the chemical formula M(amidine)_w(carboxylate)₂, wherein w is an integer from 1 to 4.

3. The silanol condensation catalyst of claim 1, wherein the metal of the one or more metal amidine complexes is zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.

4. The silanol condensation catalyst of claim 3, wherein the metal of the metal amidine complex is zinc or bismuth.

5. The silanol condensation catalyst of claim 1, wherein the one or more amine carboxylate salts is derived from a carboxylate of the following formula:

6. The silanol condensation catalyst of claim 1, wherein the one or more amine carboxylate salts is derived from an amine of general formula

R⁵¹_dYR⁵²NHR⁵³

wherein Y is O, N, S or P wherein when Y is O or S, d is 1 and when Y is N or P, d is 2;

each R⁵¹ is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms;

when d is two, R⁵¹ may be the same or different;

R⁵² is a substituted or unsubstituted bivalent hydrocarbon group having 1 to 10 carbon atoms; and

R⁵³ is a hydrogen atom or a methyl group.

8. The silanol condensation catalyst of claim 1, wherein the one or more metal amidine complexes is of the chemical formula metal (amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.

9. The silanol condensation catalyst of claim 1, wherein the one or more amine carboxylate salts is derived from amine of general formula

R⁵¹_dYR⁵²NHR⁵³

wherein Y is O, N, S or P wherein when Y is O or S, d is 1 and when Y is N or P, d is 2;

each R⁵¹ is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms;

when d is two, R⁵¹ may be the same or different;

R⁵² is a substituted or unsubstituted bivalent hydrocarbon group having 1 to 10 carbon atoms; and

R⁵³ is a hydrogen atom or a methyl group.

11. The silanol condensation catalyst of claim 1, wherein the one or more amine carboxylate salts is derived from a carboxylic acid selected from hexanoic acid, heptanoic acid 2-ethylhexanoic acid, octanoic acid, oleic acid, lauric acid, naphthenic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid.

7. A silanol condensation catalyst consisting of a mixture of one or more metal amidine complexes and one or more amine carboxylate salts, wherein the one or more amine carboxylate salts is derived from a phenyl guanidine represented by formulae

13. The silanol condensation catalyst of claim 7, wherein the one or more metal amidine complexes is of the chemical formula M(amidine)_w(carboxylate)₂, wherein w is an integer from 1 to 4.

14. The silanol condensation catalyst of claim 7, wherein the metal of the one or more metal amidine complexes is zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.

15. The silanol condensation catalyst of claim 14, wherein the metal of the metal amidine complex is zinc or bismuth.

16. The silanol condensation catalyst of claim 7, wherein the one or more metal amidine complexes is derived from an amidine of formulae I-VIII

17. The silanol condensation catalyst of claim 16, wherein the amidine of the metal amidine complex is an amidine of formula II or IV.

18. The silanol condensation catalyst of claim 17, wherein the amidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.

19. The silanol condensation catalyst of claim 7, wherein the amidine is a guanidine, wherein the guanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.

20. The silanol condensation catalyst of claim 7, wherein the amidine is at least one member selected from the group consisting of 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and 1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.

21. The silanol condensation catalyst of claim 7, wherein the amidine is at least one guanidine selected from the group consisting of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and 7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

22. The silanol condensation catalyst of claim 17, wherein the carboxylate of the metal amidine complex is heptanoate, hexanoate, laurate, oleate, versatate, octoate, neodecanoate, naphthenate, stearate, or oxalate.

23. The silanol condensation catalyst of claim 7, wherein the one or more metal amidine complexes is of the chemical formula metal (amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.

10. A silanol condensation catalyst consisting of a mixture of one or more metal amidine complexes and one or more amine carboxylate salts, wherein the one or more amine carboxylate salts is derived from an amine selected from monoethanolamine, 3-hydroxypropylamine, 2-(2-aminoethylamino)ethanol, 1-dimethylamino-2-propanol, diethylamino-2-propanol, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-dimethylamino-2-methyl-1-propanol, ethylenediamine, N-methylethylenediamine, 1, 3-propanediamine, N-methyl-1, 3-propanediamine, N, N′

-dimethyl-1, 3-propanediamine, 3-(diethylamino)propyl amine, 3-(dimethylamino)propyl amine and diethylenetriamine.

24. The silanol condensation catalyst of claim 10, wherein the one or more metal amidine complexes is of the chemical formula M(amidine)_w(carboxylate)₂, wherein w is an integer from 1 to 4.

25. The silanol condensation catalyst of claim 10, wherein the metal of the one or more metal amidine complexes is zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.

26. The silanol condensation catalyst of claim 25, wherein the metal of the metal amidine complex is zinc or bismuth.

27. The silanol condensation catalyst of claim 10, wherein the one or more metal amidine complexes is derived from an amidine of formulae I-VIII

28. The silanol condensation catalyst of claim 27, wherein the amidine of the metal amidine complex is an amidine of formula II or IV.

29. The silanol condensation catalyst of claim 10, wherein the amidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.

30. The silanol condensation catalyst of claim 10, wherein the guanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.

31. The silanol condensation catalyst of claim 10, wherein the amidine is at least one member selected from the group consisting of 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and 1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.

32. The silanol condensation catalyst of claim 10, wherein the amidine is at least one guanidine selected from the group consisting of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and 7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

33. The silanol condensation catalyst of claim 10, wherein the carboxylate of the metal amidine complex is heptanoate, hexanoate, laurate, oleate, versatate, octoate, neodecanoate, naphthenate, stearate, or oxalate.

34. The silanol condensation catalyst of claim 10, wherein the one or more metal amidine complexes is of the chemical formula metal (amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.

12. A silanol condensation catalyst consisting of a mixture of one or more metal amidine complexes and one or more amine carboxylate salts, wherein the one or more amine carboxylate salts is derived from a carboxylic acid in which the α

-carbon atom of the carboxyl group is a quaternary carbon atom.

35. The silanol condensation catalyst of claim 12, wherein the one or more metal amidine complexes is of the chemical formula M(amidine)_w(carboxylate)₂, wherein w is an integer from 1 to 4.

36. The silanol condensation catalyst of claim 12, wherein the metal of the one or more metal amidine complexes is zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.

37. The silanol condensation catalyst of claim 36, wherein the metal of the metal amidine complex is zinc or bismuth.

38. The silanol condensation catalyst of claim 12, wherein the one or more metal amidine complexes is derived from an amidine of formulae I-VIII

39. The silanol condensation catalyst of claim 38, wherein the amidine of the metal amidine complex is an amidine of formula II or IV.

40. The silanol condensation catalyst of claim 12, wherein the amidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.

41. The silanol condensation catalyst of claim 12, wherein the guanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.

42. The silanol condensation catalyst of claim 12, wherein the amidine is at least one member selected from the group consisting of 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and 1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.

43. The silanol condensation catalyst of claim 12, wherein the amidine is at least one guanidine selected from the group consisting of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and 7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

44. The silanol condensation catalyst of claim 12, wherein the carboxylate of the metal amidine complex is heptanoate, hexanoate, laurate, oleate, versatate, octoate, neodecanoate, naphthenate, stearate, or oxalate.

45. The silanol condensation catalyst of claim 12, wherein the one or more metal amidine complexes is of the chemical formula metal (amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.

46. The silanol condensation catalyst of claim 12, wherein the one or more amine carboxylate salts is derived from a carboxylic acid selected from hexanoic acid, heptanoic acid 2-ethylhexanoic acid, octanoic acid, oleic acid, lauric acid, naphthenic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid.