Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof

1. An adhesion promoting adduct having a structure of Formula (13):

R 11 —P—R 12′ —R 13′ -M-R 14   (13)

wherein,

R 11 comprises an adhesion promoting group;

P comprises a core of an adhesion promoter R 11 —P—R 12 ;

M comprises a metal ligand, wherein the metal ligand comprises a moiety of Formula (12a), Formula (12b), Formula (12c), Formula (12d), Formula (12e), or a combination of any of the foregoing:

—X—(CH 2 ) n —CH(—OH)—  (12a)

—X—(CH 2 ) n —CH(—OH)—(CH 2 ) n —X—  (12b)

—CH(—OH)—(CH 2 ) n —X—(CH 2 ) n —CH(—OH)—  (12c)

—CH(—OH)—R 5 —CH(—OH)—  (12d)

—C(O)—R 5 —C(O)—  (12e)

wherein,

each X is independently selected from —C(O)— and —S(O) 2 —,

n is an integer from 1 to 3; and

R 5 is C 1-4 alkanediyl;

R 12′ and R 13′ represent moieties derived from the reaction of R 12 and R 13 of the adhesion promoter R 11 —P—R 12 and a metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and

R 14 comprises a reactive functional group selected from a thiol group, an epoxy group, an isocyanate group, an alkenyl group, and a Michael acceptor group.

2. The adhesion promoting adduct of claim 1 , wherein R 14 comprises a Michael acceptor group.

3. The adhesion promoting adduct of claim 1 , wherein the adhesion promoting group comprises a polyalkoxysilyl, a phosphonate, an amine, a carboxylic acid, or a phosphonic acid.

4. The adhesion promoting adduct of claim 1 , wherein R 12 comprises an alkenyl group, a thiol group, or an amine group.

5. The adhesion promoting adduct of claim 1 , wherein the adhesion promoter comprises a thiol-terminated polyalkoxysilane.

6. The adhesion promoting adduct of claim 1 , wherein the adhesion promoter comprises a structure of Formula (14a), a structure of Formula (14b), a structure of Formula (14c), or a combination of any of the foregoing:

wherein

each R 16 is independently selected from C 1-3 alkyl; and

R 17 is selected from hydrogen and C 1-3 alkyl.

7. The adhesion promoting adduct of claim 1 , wherein the metal ligand comprises a bis(sulfonyl)alkanol, a quinone, an acetylacetonate, a hydroxypyridinone, or a combination of any of the foregoing.

8. The adhesion promoting adduct of claim 1 , wherein,

the adhesion promoter comprises an amino-terminated polyalkoxysilane or a thiol-terminated polyalkoxysilane; and

the metal ligand comprises a bis(sulfonyl)alkanol, a quinone, an acetylacetonate, or a hydroxypyridinone.

9. The adhesion promoting adduct of claim 1 , wherein the metal ligand comprises a group capable of forming a coordination complex with aluminum, Al(III), aluminum oxide, titanium, titanium oxide, anodized aluminum, chromate conversion coated aluminum, or a combination of any of the foregoing.

10. The adhesion promoting adduct of claim 1 , wherein the metal ligand is capable of forming a coordination complex with Al(III).

11. The adhesion promoting adduct of claim 1 , wherein the metal chelating agent comprises an aluminum oxide or Al(III) ligand selected from 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy-2-pyridinone, 2-2′-dihydroxyazobenzene, 8-hydroxyquinoline, oxylate, malonate, citrate, inimodiacetic acid, picolinic acid, maltol, kojic acid, N,N′-diacetic acid (EDTA), N-(2-hydroxy)ethylenediamenetriacetic acid (HEDTA), ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid (EDDHA), and N,N′-bis(hydroxybenzyl)ethylenediamene-N,N′-diacetic acid (HBED), acetoacetate, quinone, and a combination of any of the foregoing.

12. The adhesion promoting adduct of claim 1 , wherein —R 13′ -M-R 14 has the structure:

—CH 2 —CH 2 —S(O) 2 —R 15 —CH(—OH)—R 15 —S(O) 2 —CH═CH 2 , or

—CH 2 —CH 2 —S(O) 2 —CH 2 —CH(—OH)—CH 2 —S(O) 2 —CH═CH 2

wherein each R 15 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein the one or more substituent groups is —OH.

13. A composition comprising the adhesion promoting adduct of claim 1 .

14. A cured sealant formed from the composition of claim 13 .

15. An adhesion promoting adduct having the structure of Formula (15):

wherein each R 16 is independently selected from C 1-3 alkyl.

16. A composition comprising the adhesion promoting adduct of claim 15 .

17. A cured sealant formed from the composition of claim 16 .

18. A copolymerizable adhesion promoting adduct having the structure of Formula (21):

B(—V 1′ —R 14′ -M-R 13′ —R 12′ —P—R 11 ) z1 (—V 2 ) z-z1   (21)

wherein,

R 11 comprises an adhesion promoting group;

P comprises a core of an adhesion promoter R 11 —P—R 12 ;

M comprises a metal ligand;

R 12′ and R 13′ represent moieties derived from the reaction of R 12 and R 13 of the adhesion promoter R 11 —P—R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a reactive functional group reactive with —V 1 ;

B represents a core of a z-valent polyfunctionalizing agent of Formula (22):

B(—V 1 ) z1 (—V 2 ) z-z1   (22)

wherein,

z is an integer from 3 to 6;

z1 is an integer from 1 to z−1;

each —V 1 is a group comprising a first reactive functional group; and

at least one —V 2 comprises a thiol group, an alkenyl group, an epoxy group, an isocyanate group, or a Michael acceptor group; and

each R 14′ represents a moiety derived from the reaction of R 14 and —V′; and

each —V 1′ — and R 14′ is derived from the reaction of —V 1 with R 14 .

19. The copolymerizable adhesion promoting adduct of claim 18 , comprising the reaction product of reactants comprising:

a polyfunctionalizing agent of Formula (22):

B(—V 1 ) z1 (—V 2 ) z-z1   (22)

wherein,

B represents a core of a z-valent polyfunctionalizing agent B(—V) z

wherein:

z is an integer from 3 to 6;

z1 is an integer from 1 to z−1;

each —V 1 is a group comprising a first reactive functional group; and

at least one —V 2 comprises a thiol group, an alkenyl group, an epoxy group, an isocyanate group, or a Michael acceptor group; and

an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a third functional group reactive with the first reactive functional group.

20. A composition comprising the copolymerizable adhesion promoting adduct of claim 18 .

21. A cured sealant formed from the composition of claim 20 .

22. A copolymerizable sulfur-containing adhesion promoting adduct of Formula (23);

B(—V′—S—R 1 —S—R 14′ -M-R 13′ —R 12′ —P—R 11 ) z1 (—V′—S—R—SH) z-z1   (23)

wherein

each R 1 is independently selected from C 2-6 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[—(CHR 3 ) s —X—] q —(CHR 3 ) r —;

wherein:

each R 3 is independently selected from hydrogen and methyl;

each X is independently selected from —O—, —S—, and —NR— wherein R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5; and

r is an integer from 2 to 10;

R 11 comprises an adhesion promoting group;

P comprises a core of an adhesion promoter R 11 —P—R 12 ;

M comprises a metal ligand;

R 12′ and R 13′ represent moieties derived from the reaction of R 12 and R 13 of the adhesion promoter R 11 —P—R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a group reactive with a thiol —SH group;

R 14′ represents a moiety derived from the reaction of R 14 and a thiol group;

B represents a core of a z-valent polyfunctionalizing agent B(—V) z wherein:

z is an integer from 3 to 6;

z1 is an integer from 1 to z−1; and

each —V is a group comprising a group reactive with a thiol group; and

each —V′— and R 14′ is derived from the reaction of —V with a thiol group.

23. The copolymerizable sulfur-containing adhesion promoting adduct of claim 22 , comprising the reaction product of reactants comprising:

a dithiol;

a polyfunctionalizing agent comprising functional groups reactive with thiol groups; and

an adhesion promoting adduct comprising an adhesion promoting group and functional groups reactive with thiol groups.

24. A composition comprising the copolymerizable adhesion promoting adduct of claim 22 .

25. A cured sealant formed from the composition of claim 24 .

26. A composition comprising:

an adhesion promoting adduct; and

a sulfur-containing prepolymer,

wherein the adhesion promoting adduct comprises a structure of Formula (13):

R 11 —P—R 12′ —R 13′ -M-R 14   (13)

wherein,

R 11 comprises an adhesion promoting group;

P comprises a core of an adhesion promoter R 11 —P—R 12 ;

M comprises a metal ligand;

R 12′ and R 13′ represent moieties derived from the reaction of R 12 and R 13 of the adhesion promoter R 11 —P—R 12 and a metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and

R 14 comprises a reactive functional group selected from a thiol group, an epoxy group, an isocyanate group, an alkenyl group, and a Michael acceptor group.

27. The composition of claim 26 , wherein the sulfur-containing prepolymer comprises a thiol-terminated sulfur-containing prepolymer selected from a thiol-terminated polythioether prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated sulfur-containing polyformal prepolymer, and a combination of any of the foregoing.

28. The composition of claim 26 , wherein the sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer.

29. The composition of claim 26 , formulated as a sealant composition.

30. A cured sealant formed from the composition of claim 29 .

31. An adhesion promoting adduct having a structure of Formula (13):

R 11 —P—R 12′ —R 13′ -M-R 14   (13)

wherein,

R 11 comprises an adhesion promoting group;

P comprises a core of an adhesion promoter R 11 —P—R 12 ;

M comprises a metal ligand;

R 12′ and R 13′ represent moieties derived from the reaction of R 12 and R 13 of the adhesion promoter R 11 —P—R 12 and a metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and

R 14 comprises a vinylsulfonyl group.

32. The adhesion promoting adduct of claim 31 , wherein the adhesion promoting group comprises a polyalkoxysilyl, a phosphonate, an amine, a carboxylic acid, or a phosphonic acid.

33. The adhesion promoting adduct of claim 31 , wherein R 12 comprises an alkenyl group, a thiol group, or an amine group.

34. The adhesion promoting adduct of claim 31 , wherein the adhesion promoter comprises a thiol-terminated polyalkoxysilane.

35. The adhesion promoting adduct of claim 31 , wherein the adhesion promoter comprises a structure of Formula (14a), a structure of Formula (14b), a structure of Formula (14c), or a combination of any of the foregoing:

wherein

each R 16 is independently selected from C 1-3 alkyl; and

R 17 is selected from hydrogen and C 1-3 alkyl.

36. The adhesion promoting adduct of claim 31 , wherein the metal ligand comprises a bis(sulfonyl)alkanol, a quinone, an acetylacetonate, a hydroxypyridinone, or a combination of any of the foregoing.

37. The adhesion promoting adduct of claim 31 , wherein,

the adhesion promoter comprises an amino-terminated polyalkoxysilane or a thiol-terminated polyalkoxysilane; and

the metal ligand comprises a bis(sulfonyl)alkanol, a quinone, an acetylacetonate, or a hydroxypyridinone.

38. The adhesion promoting adduct of claim 31 , wherein the metal ligand comprises a group capable of forming a coordination complex with aluminum, Al(III), aluminum oxide, titanium, titanium oxide, anodized aluminum, chromate conversion coated aluminum, or a combination of any of the foregoing.

39. The adhesion promoting adduct of claim 31 , wherein the metal ligand is capable of forming a coordination complex with Al(III).

40. The adhesion promoting adduct of claim 31 , wherein the metal chelating agent comprises an aluminum oxide or Al(III) ligand selected from 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy-2-pyridinone, 2-2′-dihydroxyazobenzene, 8-hydroxyquinoline, oxylate, malonate, citrate, inimodiacetic acid, picolinic acid, maltol, kojic acid, N,N′-diacetic acid (EDTA), N-(2-hydroxy)ethylenediamenetriacetic acid (HEDTA), ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid (EDDHA), and N,N′-bis(hydroxybenzyl)ethylenediamene-N,N′-diacetic acid (HBED), acetoacetate, quinone, and a combination of any of the foregoing.

41. The adhesion promoting adduct of claim 31 , wherein —R 13′ -M-R 14 has the structure:

—CH 2 —CH 2 —S(O) 2 —R 15 —CH(—OH)—R 15 —S(O) 2 —CH═CH 2 , or

—CH 2 —CH 2 —S(O) 2 —CH 2 —CH(—OH)—CH 2 —S(O) 2 —CH═CH 2

wherein each R 15 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein the one or more substituent groups is —OH.

42. A composition comprising the adhesion promoting adduct of claim 31 .

43. A cured sealant formed from the composition of claim 42 .