Composition including a polyorganosiloxane and an amino-functional silane and method of using the same
The composition includes a polyorganosiloxane and an amino-functional silane. The polyorganosiloxane has divalent units represented by Formula (I) and greater than two —Si(Y) p (R) 3-P groups, in which each R is a non-hydrolyzable group; each Y is a hydrolysable group; and p is 1, 2, or 3. The composition further includes an amino-functional silane represented by (R 6 ) 2 N—[R 4 —Z] r —R 4 —[Si(Y) p (R 5 ) 3-P ] or a cyclic azasilane of Formula (II). Each R 4 is a linking group; each R 5 is a non-hydrolyzable group; each Z is —O— or —N(R 6 )—; each R 6 is hydrogen, alkyl, aryl, arylalkylenyl, or —R 4 —[Si(Y) p (R 5 ) 3-P ]; R 7 is a linking group that can have at least one catenated —N(R 8 )—; each R 8 is hydrogen, alkyl, or alkenyl, which may be substituted by an amino group; each Y is a hydrolyzable group; r is 0, 1, 2, or 3; and p is 1, 2, or 3. A method of using the composition to make a coated article is also described.
1. A composition comprising:
a first polyorganosiloxane comprising divalent units represented by formula:
and greater than two —Si(Y) p (R) 3-p groups,
wherein the first polyorganosiloxane comprises (m) terminal units represented by formula —Q—Si(Y) p (R) 3-p and (n) divalent units represented by formula:
wherein
each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
each Q is independently a bond, alkylene, arylene, or alkylene that is at least one of interrupted or terminated by aryl, wherein the alkylene, arylene, and alkylene that is at least one of interrupted or terminated by aryl are optionally at least one of interrupted or terminated by at least one ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, thiourea, or a combination thereof;
each Y is independently a hydrolyzable group;
p is 1, 2, or 3;
(n) is at least 1; and
(m)+(n) is in a range from 3 to 6; and
at least one of
an amino-functional silane represented by formula (R 6 ) 2 N—[R 4 —Z] r —R 4 —[Si(Y) p (R 5 ) 3-p ] or a cyclic azasilane represented by formula
wherein
each R 4 is independently alkylene, arylene, or alkylene optionally interrupted or terminated by arylene;
R 5 is alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
each Z is independently —O— or —N(R 6 )—;
each R 6 is independently hydrogen, alkyl, aryl, arylalkylenyl, or —R 4 —[Si(Y) p (R 5 ) 3-p ], wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
R 7 is an alkylene having 2 to 5 carbon atoms and is uninterrupted or interrupted by at least one catenated —N(R 8 )—;
each R 8 is independently hydrogen, alkyl, or alkenyl, wherein alkyl and alkenyl are unsubstituted or substituted by —NR 1 R 2 , wherein R 1 and R 2 are independently hydrogen or alkyl;
each Y is independently a hydrolyzable group;
r is 0, 1, 2, or 3; and
p is 1, 2, or 3,
wherein when the composition is applied to a surface of a substrate and at least partially cured to form a coated surface, the coated surface has a receding deionized water contact angle of greater than 80 after 500 scrubs using the Panel Scrub Method.
2. The composition of claim 1 , wherein the ratio of divalent units represented by formula:
to —Si(Y) p (R) 3-p groups is at least 4.
3. The composition of claim 1 , wherein the first polyorganosiloxane further comprises at least one terminal —Si(R) 3 group, wherein each R is independently alkyl or phenyl.
4. The composition of claim 1 , wherein each Y is methoxy, and wherein the first polyorganosiloxane has a weight percent of methoxy groups of not more than 20 weight percent, based on the total weight of the first polyorganosiloxane.
5. The composition of claim 1 , further comprising a silane represented by formula:
R 3 f [Si(X) 4-f ] g
wherein:
g is 1 to 6;
f is 0, 1, or 2, with the proviso that when f is 0, g is 1;
each R 3 is monovalent or multivalent and is independently alkyl, aryl, or arylalkylenyl, wherein alkyl and arylalkylenyl are each uninterrupted or interrupted with at least one catenated —O—, —N(R 11 )—, —S—, —P—, —Si— or combination thereof, wherein aryl and arylalkylenyl are each unsubstituted or substituted by alkyl or alkoxy, and wherein alkyl, aryl, and arylalkylenyl are each unsubstituted or substituted with at least one epoxy, thiol, (meth)acrylate, vinyl, allyl, isocyanate, thiocyanate, ureido, chloro, or a combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof; and
each X is independently hydroxyl or a hydrolyzable group.
6. The composition of claim 1 , further comprising a catalyst for at least one of hydrolyzing the Y groups in at least one of the first polyorganosiloxane, amino-functional silane, or cyclic azasilane or condensing silanol groups to form siloxane bonds.
7. The composition of claim 1 , further comprising a second polyorganosiloxane comprising divalent units represented by formula:
wherein each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof, and wherein the second polyorganosiloxane does not include hydrolyzable groups.
8. The composition of claim 1 , further comprising a third polyorganosiloxane comprising divalent units represented by formula:
and at least one —Si(Y) p (R) 3-p group,
wherein each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
9. The composition of claim 1 , wherein the amino-functional silane is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, N-methyl-bis(3-trimethoxysilylpropyl)amine, N-methyl-bis(3-triethoxysilylpropyl)amine, [3-(2-aminoethylamino)propyl]trimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, [3-(2-aminoethylamino)propyl]triethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxysilane, N,N′-bis[3-trimethoxysilylpropyl]-ethylenediamine, N,N-bis[3-trimethoxysilylpropyl]-ethylenediamine, or a combination thereof, and wherein the cyclic azasilane is 2,2-dimethoxy-N-butyl-1-aza-2-silacyclopentane, 2-methyl-2-methoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-N-allyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-methyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-aza-2-silacyclopentane, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, N-methyl-1-aza-2,2,4-trimethylsilacyclopentane, or a combination thereof.
10. The composition of claim 1 , wherein the first polyorganosiloxane is a linear polyorganosiloxane.
11. The composition of claim 1 , wherein the composition is at least one of essentially free of fluorinated silanes, comprises not more than five percent by weight water, based on the total weight of the composition, or comprises not more than 20 percent by weight organic solvent, based on the total weight of the composition.
12. A composition: comprising water:
at least one of a nonionic surfactant or an anionic surfactant;
a first polyorganosiloxane comprising divalent units represented by formula:
and greater than two —Si(Y) p (R) 3-p groups, wherein
each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—,—N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 1 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
each Y is independently a hydrolyzable group; and
pis 1, 2, or 3; and
at least one of
an amino-functional silane represented by formula (R 6 ) 2 N-[R 4 -Z]- r- R 4 -[Si(Y) p (R 5 ) 3-p ] or a cyclic azasilane represented by formula
wherein
each R 4 is independently alkylene, arylene, or alkylene optionally interrupted or terminated by arylene;
R 5 is alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
each Z is independently —O— or —N(R 6 )—;
each R 6 is independently hydrogen, alkyl, aryl, arylalkylenyl, or —R 4 —[Si(Y) p (R 5 ) 3-p ], wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
R 7 is an alkylene having 2 to 5 carbon atoms and is uninterrupted or interrupted by at least one catenated —NR(R 8 )—;
each R 8 is independently hydrogen, alkyl, or alkenyl, wherein alkyl and alkenyl are unsubstituted or substituted by —NR 1 R 2, wherein R 1 and R 2 are independently hydrogen or alkyl;
each Y is independently a hydrolyzable group;
r is 0, 1, 2, or 3; and
p is 1, 2, or 3.
13. A method of making a coated article, the method comprising:
applying the composition of claim 1 on at least a portion of a surface of a substrate; and
allowing or inducing the composition to at least partially cure to form a coating on at least a portion of the surface of the substrate.
14. The method of claim 13 , further comprising removing a portion of the composition from the surface of the substrate before allowing or inducing the composition to fully cure.
15. The method of claim 13 , wherein the substrate is at least a portion of a vehicle.
16. A coated article made by the method of claim 13 .
17. The composition of claim 1 , wherein the first polyorganosiloxane comprises not more than two terminal units represented by formula -Q-Si(Y) p (R) 3-p .
18. The composition of claim 1 , wherein each Y is independently alkoxy, aryloxy, or acyloxy.
19. The composition of claim 12 , wherein the ratio of divalent units represented by formula:
to —Si(Y) p (R) 3-p groups is at least 4.
20. The composition of claim 12 , wherein the first polyorganosiloxane comprises (m) terminal units represented by formula -Q-Si(Y) p (R) 3-p and (n) divalent units represented by formula:
wherein
each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof;
each Q is independently a bond, alkylene, arylene, or alkylene that is at least one of interrupted or terminated by aryl, wherein the alkylene, arylene, and alkylene that is at least one of interrupted or terminated by aryl are optionally at least one of interrupted or terminated by at least one ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, thiourea, or a combination thereof;
each Y is independently a hydrolyzable group;
p is 1, 2, or 3;
(n) is at least 1; and
(m)+(n) is greater than 2.
21. The composition of claim 20 , wherein (m)+(n) is in a range from 3 to 6.
22. The composition of claim 12 , wherein the first polyorganosiloxane further comprises at least one terminal —Si(R) 3 group, wherein each R is independently alkyl or phenyl.
23. The composition of claim 12 , wherein each Y is methoxy, and wherein the first polyorganosiloxane has a weight percent of methoxy groups of not more than 20 weight percent, based on the total weight of the first polyorganosiloxane.
24. The composition of claim 12 , further comprising a silane represented by formula:
R 3 f [Si(X) 4-n ] g
wherein:
g is 1 to 6;
f is 0, 1, or 2, with the proviso that when fis 0, g is 1;
each R 3 is monovalent or multivalent and is independently alkyl, aryl, or arylalkylenyl, wherein alkyl and arylalkylenyl are each uninterrupted or interrupted with at least one catenated —O—,—N(R 11 )—, —S—, —P—, —Si— or combination thereof, wherein aryl and arylalkylenyl are each unsubstituted or substituted by alkyl or alkoxy, and wherein alkyl, aryl, and arylalkylenyl are each unsubstituted or substituted with at least one epoxy, thiol, (meth) acrylate, vinyl, allyl, isocyanate, thiocyanate, ureido, chloro, or a combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof; and
each X is independently hydroxyl or a hydrolyzable group.
25. The composition of claim 12 , further comprising a catalyst for at least one of hydrolyzing the Y groups in at least one of the first polyorganosiloxane, amino-functional silane, or cyclic azasilane or condensing silanol groups to form siloxane bonds.
26. The composition of claim 12 , further comprising a second polyorganosiloxane comprising divalent units represented by formula:
wherein each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof, and wherein the second polyorganosiloxane does not include hydrolyzable groups.
27. The composition of claim 12 , further comprising a third polyorganosiloxane comprising divalent units represented by formula:
and at least one —Si(Y) p (R) 3-p group,
wherein each R is independently alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl, wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated —O—, —S—, —N(R 11 )—, or combination thereof, wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof, and wherein R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
28. The composition of claim 12 , wherein the amino-functional silane is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, N-methyl-bis(3-trimethoxysilylpropyl)amine, N-methyl-bis(3-triethoxysilylpropyl)amine, [3-(2-aminoethylamino)propyl] trimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino] propyltrimethoxysilane, [3-(2-aminoethylamino) propyl] triethoxysilane, 3-[2-(2-aminoethylamino) ethylamino] propyltriethoxysilane, N,N′-bis [3-trimethoxysilylpropyl]-ethylenediamine, N,N-bis [3-trimethoxysilylpropyl]-ethylenediamine, or a combination thereof, and wherein the cyclic azasilane is 2,2-dimethoxy-N-butyl-1-aza-2-silacyclopentane, 2-methyl-2-methoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-N-allyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-methyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-aza-2-silacyclopentane, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, N-methyl-1-aza-2,2,4-trimethylsilacyclopentane, or a combination thereof.
29. The composition of claim 12 , wherein the first polyorganosiloxane is a linear polyorganosiloxane.
30. The composition of claim 12 , wherein each Y is independently alkoxy, aryloxy, or acyloxy.