Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes

• US 9,718,989 B1
• Filed: 01/19/2017
• Issued: 08/01/2017
• Est. Priority Date: 06/03/2016
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Palsule, Aniruddha S., Vanderpool, Katherine E., Deshpande, Anushree, Klier, John, Sullivan, Jeffrey M., Holzer, Alexander R.
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US15/410,003
• Time in Patent Office: 194 Days
• Field of Search: None
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08G 63/52 Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• CPC Class Codes: C08G 63/553 Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
• CPC Class Codes: C08G 63/676 in which at least one of the two components contains aliphatic unsaturation
• CPC Class Codes: C08G 63/78 Preparation processes
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 67/06 Unsaturated polyesters
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 79/02 Polyamines
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 133/06 of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09D 167/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C09D167/06 takes precedence
• CPC Class Codes: C09D 167/06 Unsaturated polyesters having carbon-to-carbon unsaturation
• CPC Class Codes: C12P 7/625 Polyesters of hydroxy carboxylic acids

Abstract

Compositions comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols; and b) one or more polymers having pendant Michael Addition donor groups. Disclosed are coating prepared from these compositions.

Claims

1. A composition comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters ore 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or more diols:

and b) one or more polymers having pendant Michael Addition donor groups wherein a portion of or all of the polyester macromers are crosslinked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1-alkene groups of the polyester macromers

wherein the crosslinks by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1-alkene groups of the polyester macromer correspond to the formula

2. A composition according to claim 1 wherein X is independently in each occurrence O, NR^y, or S;

R^x is independently in each occurrence a polymer comprising an acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer poly, polyester polyol, polyether polyol or siloxane polyol or a substrate; and

,

R^y is independently in each occurrence H or a hydrocarbyl group.

3. A composition according to claim 1 wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

4. A composition according to claim 1 wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

5. A composition according to claim 1 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols.

6. A composition according to claim 1 wherein the one or more polymers having Pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols.

7. A composition according to claim 1 wherein the polyester macromer exhibits a number average molecular weight of about 400 to about 3000.

17. A composition according to claim 1 wherein a portion of the polyester macromers are crosslinked through some of the 1,1-alkene groups wherein the crosslinks between chains are represented by formula 17:

18. A composition according to claim 17 wherein F is separately in each occurrence a direct bond or the residue of a 1,1-diester-1-alkene or a multifunctional monomer.

8. A composition comprising

i) a plurality of polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more dole and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or morn diols;

ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes;

iii) one or more 1,1-diester-1-alkenes; and

iv) one or more polymers having pendant Michael Addition donor groups;

wherein a portion of or all of the polyester macromers are crosslinked through the 1,1-alkene groups by Michael Addition of the Michael Addition Donors pendant from the polymers;

wherein the crosslinks by Michael Addition of the Michael Addition Donors pendant from the polyols to the 1-alkene groups of the polyester macromer correspond to the formula

9. A composition according to claim 8 wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

10. A composition according to claim 8 wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

11. A composition according to claim 8 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols.

12. A composition according to claim 8 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols.

13. A composition according to claim 8 wherein X is independently in each occurrence O, NR^y, or S;

and

R^x is independently in each occurrence a polymer comprising an acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, polyester polyol, polyether polyol or silane polyol or a substrate; and

,

R^y is H or a hydrocarbyl group.

14. A composition according to claim 8 wherein a portion of the polyester macromers are crosslinked through some of the 1,1-alkene groups wherein the crosslinks between chains are represented by formula 17:

15. A composition according to claim 14 wherein F is separately in each occurrence a direct bond or the residue of a 1,1-diester-1-alkene or a multifunctional monomer.

16. A composition according to claim 8 wherein the polyester macromer exhibits a number average molecular weight of about 400 to about 3000.