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

• US 9,567,475 B1
• Filed: 10/20/2016
• Issued: 02/14/2017
• Est. Priority Date: 06/03/2016
• Status: Active Grant

• Current Assignee: 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 A
• Application Number:
  US15/298,637
• Time in Patent Office: 117 Days
• Field of Search: None
• US Class Current: 1/1
• 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) a polyester macromer composition comprising 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.

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

3. A composition according to claim 2 wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

4. 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.

5. 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.

6. A composition according to claim 1 which comprises from about 40 to about 90 percent by weight of the one or more polyester macromers and from about 10 to 60 percent by weight of the one or more one or more polymers having pendant Michael Addition donor groups wherein the amounts are based on the weight of the composition.

7. A composition according to claim 6 which contains a solvent which comprises one or more polar aprotic solvents.

8. A composition according to claim 1 wherein the polyester macromer exhibits a number average molecular weight of about 700 to about 3000.

9. A composition according to claim 1 wherein the polyester macromer composition comprises:

i) a plurality of polyester macromers;

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; and

iii) one or more 1,1-diester-1-alkenes.

10. A composition according to claim 9 wherein the polyester macromer composition comprises

i) from about 10 to about 90 percent by weight of the plurality of polyester macromers;

ii) from about 1 to about 50 percent by weight of the one or more multifunctional monomers; and

iii) from about 1 to about 30 percent by weight of the one or more 1,1-diester-1-alkenes wherein the percentages are based on the amounts of the ingredients listed.

11. A composition according to claim 1 wherein the polymers having pendant Michael Addition donor groups exhibit a hydroxyl number of about 50 to about 200.

12. A coating obtained by curing a composition according to claim 1.

13. The coating according to claim 12 having a thickness of about 2 to about 160 microns.

14. The coating according to claim 12 wherein the polyester macromers are crosslinked through the 1,1-alkene groups and/or by Michael Addition of the Michael Addition donor groups pendant from the polymers having pendant Michael Addition Donor groups to the 1-alkene groups.

15. The coating according to claim 12 wherein the cured coating exhibits one or more of the following properties of a gloss according to ASTM D523-08 at 20°

, or 60°

, or 85°

of 40 GU or greater;

a pencil hardness according to ASTM D3363-00 of 3H or greater;

a solvent resistance according to ASTM D5402-93 to 80 rubs of methyl ethyl ketone or greater;

mandrel flexibility according to ASTM D522-93 of 80 percent or greater;

cross hatch adhesion of 4B or higher and 100 percent according to ASTM D3359-09 and acid resistance up to 70°

C. and base resistance at greater than 70°

C. according to GMW 14701.

16. A method comprising contacting a composition according to claim 1 with a surface of a substrate wherein the surface is at least mildly nucleophilic and forming a coating on the surface of the substrate comprising the composition containing the one or more polyester macromers.

17. A method according to claim 16 wherein the substrate has a pigmented coating deposited on its surface wherein the pigmented coating is mildly basic or nucleophilic.

18. A method according to claim 16 which includes exposing the substrate with the composition containing one or more polyester macromers deposited on the substrate to a temperature of about 20°

C. to about 150°

C. for about 10 minutes to about 120 minutes under conditions such that the coating containing one or more polyester macromers disposed on the surface of the substrate is crosslinked.

19. A method according to claim 16 wherein the coating or the surface of the substrate contains a catalyst for Michael Addition.

20. A method according to claim 16 wherein the coating on the surface of the substrate contains an initiator for anionic polymerization.