Water reducible coating compositions including carboxy ester ketals, methods of manufacture, and uses thereof
A water-reducible coating composition includes a water-reducible polymer binder; water; and a ketal adduct of formula (1) as well as coated substrates and films formed from the compositions. The films are useful as paints, stains, and clear-coats.
1. A water-reducible coating composition, comprising:
a water-reducible polymer binder;
water; and
a ketal adduct of formula (1)
wherein
R 1 is C1-6 alkyl, C2-6 alkenyl, C3-6 cycloalkyl, C5-6 cycloalkenyl, C6-12 aryl, C7-C13 arylalkylene, or —(CH 2 ) s OR 8 wherein s is 1-3 and R 8 is C1-6 alkyl or (OCH 2 CH 2 ) t OCH 2 CH 3 wherein t is 1-10,
R 2 is hydrogen or C1-14 alkyl,
R 3 is hydrogen or C1-6 alkyl,
each R 4 and R 5 is independently
hydrogen, C1-6 alkyl, C1-6 alkyl substituted with up to four OR 9 groups wherein R 9 is hydrogen, C1-6 alkyl, or C(O)R 10 wherein R 10 is C1-6 alkyl, or
R 4 and R 5 taken together are a double-bonded oxygen, or
when b is 1, R 3 and R 4 together with their directly attached carbons form a fused cycloaliphatic ring having a total of 5-6 carbon atoms or 4-5 carbon atoms and 1-2 oxygen atoms,
R 6 is
hydrogen, C1-6 alkyl, or hydroxymethylene, or
when b is 0, R 3 and R 6 together with their directly attached carbons form a fused cycloaliphatic or aromatic ring having a total of 5-6 carbon atoms or 4-5 carbon atoms and 1-2 oxygen atoms,
R 7 is
hydrogen, C1-6 alkyl, C1-6 alkyl substituted with up to four OR 8 groups wherein R 8 is hydrogen, C1-6 alkyl, or C(O)R 10 wherein R 10 is C1-6 alkyl, or
C5-6 cylcoalkyl that is optionally substituted with an oxygen in the ring and further optionally substituted with 1-2 hydroxyl or OR 11 wherein R 11 is C1-3 alkyl,
a is 0-6, and
b is 0-1,
wherein the composition comprises about 0.1 to about 30 wt. % of the ketal adduct, based on the weight of the water-reducible polymer binder.
2. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-6 alkyl or C7-C13 arylalkylene,
R 2 is C1-6 alkyl,
R 3 is hydrogen or C1-3 alkyl,
R 4 and R 5 is each independently hydrogen, C1-3 alkyl, or C1-4 alkyl substituted with 1-4 —OR 9 groups wherein R 9 is a hydrogen or C1-3 alkyl,
R 6 is hydrogen, C1-3 alkyl, or hydroxymethylene,
R 7 is hydrogen, C1-4 alkyl, or C1-4 alkyl substituted with 1-4 —OR 9 groups wherein R 9 is a hydrogen or C1-3 alkyl,
a is 1-3, and
b is 0-1.
3. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-6 alkyl,
R 2 is methyl,
R 3 , R 4 , and R 5 are each independently hydrogen, C1-4 alkyl, or C1-4 alkyl substituted with 1-2 —OR 9 groups wherein R 9 is hydrogen or a C1-3 alkyl group,
R 6 is hydrogen,
R 7 is hydrogen, C1-4 alkyl, or C1-4 alkyl substituted with 1-4 —OR 9 groups wherein R 9 is hydrogen or methyl,
a is 1-3, and
b is 0-1.
4. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-6 alkyl,
R 2 is methyl,
R 3 , R 4 , and R 6 are each independently a hydrogen or a C1-3 alkyl,
R 5 is a hydrogen, C1-4 alkyl, or C1-4 alkyl substituted with 1-2 OR 9 groups wherein R 9 is a hydrogen or C1-3 alkyl,
R 7 is a hydrogen, C1-4 alkyl, or C1-4 alkyl substituted with 1-4 —OR 9 groups wherein R 9 is hydrogen or C1-3 alkyl,
a is 1-3, and
b is 0-1.
5. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-4 alkyl,
R 2 is methyl,
R 3 is hydrogen,
R 4 is hydrogen,
R 5 is hydrogen, C1-3 alkyl, or C1-3 alkyl substituted with 1-2 —OR 9 groups wherein R 9 is hydrogen or methyl,
R 6 is hydrogen,
R 7 is hydrogen, C1-3 alkyl, or C1-3 alkyl substituted with 1-2 —OR 10 groups wherein each R 10 is independently a hydrogen or methyl,
wherein one of R 5 and R 7 is hydrogen,
a is 1-2, and
b is 0-1.
6. The water-reducible coating composition of claim 1 ,
wherein
R 1 is C1-4 alkyl,
R 2 is methyl,
R 3 is hydrogen,
R 6 is hydrogen, or C1-3 alkyl,
R 7 is hydrogen, C1-3 alkyl, or C1-4 alkyl substituted with 1-2 OR 10 groups wherein R 10 is a hydrogen or C1-3 alkyl,
a is 1-2, and
b is 0.
7. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-4 alkyl,
R 2 is methyl,
R 3 is hydrogen,
R 6 is hydrogen, methyl, or ethyl,
R 7 is methyl, ethyl, —CH 2 OH, —CH 2 OCH 3 , or —CH 2 OCH 2 CH 3 , —CH(OH)CH 2 OH, or —(CH(OH)) 3 CH 2 OH,
a is 2, and
b is 0.
8. The water-reducible coating composition of claim 1 , wherein
R 1 is C1-4 alkyl,
R 2 is methyl,
R 3 is hydrogen,
R 4 is hydrogen, methyl, ethyl, —CH 2 OH, or CH 2 OCH 3 , —CH 2 OCH 2 CH 3 ,
R 5 is hydrogen, methyl, ethyl, —CH 2 OH, —CH 2 OCH 3 , —CH 2 OCH 2 CH 3 , —CH(OH)CH 2 OH, or —(CH(OH)) 3 CH 2 OH,
R 6 is hydrogen or C1-3 alkyl,
R 7 is hydrogen or C1-3 alkyl,
a is 2, and
b is 1.
9. The water-reducible coating composition of claim 1 ,
wherein the ketal adduct is of formula (1a)
wherein R 1 is a C1-4 alkyl and R 9 is hydrogen or C1-4 alkyl.
10. The water-reducible coating composition of claim 1 ,
wherein the ketal adduct is of formula (1b)
wherein R 1 is a C1-4 alkyl.
11. The water-reducible coating composition of claim 1 , comprising about 1 to about 10 wt. % of the ketal adduct, based on the weight of the water-reducible polymer binder.
12. The water-reducible coating composition of claim 1 , wherein the water-reducible polymer binder composition comprises an acrylic, polyester, polyurethane, alkyd, silicone-modified alkyd, epoxy, epoxy ester, alkyds, or a combination thereof.
13. The water-reducible coating composition of claim 1 , wherein the water-reducible polymer binder comprises a polyurethane or alkyd.
14. The water-reducible coating composition of claim 1 , further comprising a pigment.
15. A method of preparing the water-reducible coating composition of claim 1 , comprising:
combining the water-reducible polymer binder, the ketal adduct of formula 1, and an aqueous phase.
16. The method of claim 15 , wherein the combining is by synthesizing the water-reducible polymer binder in the presence of the ketal adduct, prior to combining with the aqueous phase.
17. The method of claim 15 , comprising combining the ketal adduct and the water-reducible polymer binder after synthesis of the water-reducible polymer binder.
18. The method of claim 17 , wherein the combining comprises combining the ketal adduct and the water-reducible polymer binder prior to combining with an aqueous phase.
19. The method of claim 17 , wherein the combining comprises combining the water-reducible polymer binder and the aqueous phase, prior to combining with the ketal adduct.
20. A method of coating a substrate, comprising:
contacting the water-reducible coating composition of claim 1 with a surface of the substrate to form a coating; and
drying the coating.
21. The method of claim 20 , further comprising allowing the coating composition to at least partially impregnate the substrate.
22. A coated substrate, comprising:
a substrate having a surface; and
a coating disposed on the surface, wherein the coating comprises
a water-reducible polymer binder;
a pigment; and
a ketal adduct of claim 1 .
23. The coated substrate of claim 22 , wherein the coating at least partially impregnates the substrate, and conforms to an interior surface of the substrate.
24. The coated substrate of claim 22 , wherein the coating is a dried film.
25. A water-reducible coating composition, comprising:
a water-reducible polymer binder;
water; and
a ketal adduct of formula (1)
wherein
R 1 is C1-4 alkyl,
R 2 is methyl,
R 3 is hydrogen,
R 4 is hydrogen, methyl, ethyl, —CH 2 OH, or CH 2 OCH 3 , —CH 2 OCH 2 CH 3 ,
R 5 is hydrogen, methyl, ethyl, —CH 2 OH, —CH 2 OCH 3 , —CH 2 OCH 2 CH 3 , —CH(OH)CH 2 OH, or —(CH(OH)) 3 CH 2 OH,
R 6 is hydrogen or C1-3 alkyl,
R 7 is hydrogen or C1-3 alkyl,
a is 2, and
b is 1.
26. The water-reducible coating composition of claim 25 , wherein the composition comprises about 1 to about 10 wt. % of the ketal adduct, based on the weight of the water-reducible polymer binder.
27. The water-reducible coating composition of claim 25 , wherein the water-reducible polymer binder composition comprises an acrylic, polyester, polyurethane, alkyd, silicone-modified alkyd, epoxy, epoxy ester, alkyds, or a combination thereof.
28. The water-reducible coating composition of claim 25 , wherein the water-reducible polymer binder comprises a polyurethane or alkyd.
29. The water-reducible coating composition of claim 25 , further comprising a pigment.
30. A method of preparing the water-reducible coating composition of claim 25 , comprising:
combining the water-reducible polymer binder, the ketal adduct of formula 26, and an aqueous phase.
31. A method of coating a substrate, comprising:
contacting the water-reducible coating composition of claim 25 with a surface of the substrate to form a coating; and
drying the coating.
32. A coated substrate, comprising:
a substrate having a surface; and
a coating disposed on the surface, wherein the coating comprises
a water-reducible polymer binder;
a pigment; and
a ketal adduct of claim 25 .
33. The coated substrate of claim 32 , wherein the coating at least partially impregnates the substrate, and conforms to an interior surface of the substrate.
34. The coated substrate of claim 32 , wherein the coating is a dried film.
35. A water-reducible coating composition, comprising:
a water-reducible polymer binder;
water; and
a ketal adduct of formula (1b)
wherein R 1 is a C1-4 alkyl.
36. The water-reducible coating composition of claim 35 , wherein the composition comprises about 1 to about 10 wt. % of the ketal adduct, based on the weight of the water-reducible polymer binder.
37. The water-reducible coating composition of claim 35 , wherein the water-reducible polymer binder composition comprises an acrylic, polyester, polyurethane, alkyd, silicone-modified alkyd, epoxy, epoxy ester, alkyds, or a combination thereof.
38. The water-reducible coating composition of claim 35 , wherein the water-reducible polymer binder comprises a polyurethane or alkyd.
39. The water-reducible coating composition of claim 35 , further comprising a pigment.
40. A method of preparing the water-reducible coating composition of claim 35 , comprising:
combining the water-reducible polymer binder, the ketal adduct of formula 36, and an aqueous phase.
41. A method of coating a substrate, comprising:
contacting the water-reducible coating composition of claim 35 with a surface of the substrate to form a coating; and
drying the coating.
42. A coated substrate, comprising:
a substrate having a surface; and
a coating disposed on the surface, wherein the coating comprises
a water-reducible polymer binder;
a pigment; and
a ketal adduct of claim 35 .
43. The coated substrate of claim 35 , wherein the coating at least partially impregnates the substrate, and conforms to an interior surface of the substrate.
44. The coated substrate of claim 35 , wherein the coating is a dried film.