Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes

• US 9,617,377 B1
• Filed: 08/11/2016
• Issued: 04/11/2017
• Est. Priority Date: 06/03/2016
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: King, Elliott, Palsule, Aniruddha, Sullivan, Jeffrey M., Parab, Kshitij K., Barrett, William
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/234,191
• Time in Patent Office: 243 Days
• Field of Search: None
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C08G 63/16 Dicarboxylic acids and dihydroxy compounds
• 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 63/60 derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/87 Non-metals or inter-compounds thereof boron C08G63/84
• CPC Class Codes: C08G 64/42 Chemical after-treatment
• CPC Class Codes: C09D 167/06 Unsaturated polyesters having carbon-to-carbon unsaturation
• CPC Class Codes: C12P 7/62 Carboxylic acid esters
• CPC Class Codes: C12P 7/625 Polyesters of hydroxy carboxylic acids

Abstract

Disclosed are compositions comprising polyester macromers containing in one or more chains 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 optionally one or more dihydrocarbyl dicarboxylates, 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. The chains may contain the residue of the one or more diols and one or more diesters comprising one or more diesters 1,1-diester-1 alkenes and optionally one or more dihydrocarbyl dicarboxylates randomly disposed along the chains. Disclosed are methods of preparing the polyester macromers and incorporating them in a variety of polyester containing compositions such as coatings and films.

Claims

1. A composition comprising

i) from about 10 to about 80 percent by weight of a composition comprising 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 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;

ii) from about 5 to about 40 percent by weight of 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) from about 1 to about 40 percent by weight of one or more 1,1-diester-1-alkenes;

wherein the amounts are based on the weight of the composition.

2. A composition according to claim 1 wherein the polyester macromer contains three or more alternating chains of the residue of one or more diols and one or more diesters wherein each of the chains are bonded at one end to an oxygen of the residue of a polyol having three or more of the oxygen atoms.

3. A composition according to claim 1 wherein the polyester macromer corresponds to Formula 1

4. A composition according to claim 1 which exhibits a number average molecular weight of about 600 to about 3000.

5. A composition according to claim 1 wherein the one or more chains further comprise the residue of one or more dihydrocarbyl dicarboxylates.

6. A composition according to claim 5 wherein the polyol corresponds to the formula;

7. A composition comprising:

a) about 10 to about 80 percent by weight of a composition according claim 1;

b) from about 5 to about 40 percent by weight of a volatile solvent;

c) from about 1 to about 40 percent by weight one or more 1,1-diester-1-alkenes;

d) from about 0.01 to about 2 percent by weight of one or more wetting and levelling agents;

e) from about 0.01 to about 2 percent by weight of one or more UV stabilizers; and

,

f) from about 0.01 to about 2 percent by weight of one or more defoamers;

wherein the amounts are based on the weight of the composition.

10. A film or coating prepared by curing a composition according to claim 1.

11. A film or coating according to claim 10 having a thickness of about 0.001 micrometers to about 160 micrometers.

12. A film or coating according to claim 10 wherein the polyester macromers are crosslinked through the 1,1-alkene group.

13. A composition comprising a composition according to claim 1 in one part and in a second part one or more compounds having basic character sufficient to initiate anionic polymerization of the polyester macromers;

wherein when the two parts are combined the polyester macromers undergo curing.

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

or ii) a surface of the substrate having a composition that contains a mildly basic compound applied to the surface of the substrate before contacting the composition containing one or more polyester macromers.

19. A method according to claim 18 which includes exposing the substrate with the composition containing one or more polyester macromers 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.

8. A composition comprising from about 10 to about 80 percent by weight of 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 about 1 to about 20 percent by weight of one or more polyols having 2 or more chains and the residue of one or more 1,1-disubstituted alkenes at the terminal end of one or more of the chains;

wherein the amounts are based on the weight of the composition.

9. A composition according to claim 8 which contains a solvent and the solvent is present in an amount of about 5 to 40 percent by weight;

wherein the amounts are based on the weight of the composition.

14. A method comprising:

contacting one or more polyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more polyols having two or more of their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes; and

contacting the multifunctional monomers with an additional amount of the one or more polyols, with the proviso that the additional amount of the one or more polyols are diols, or with one or more second polyols which are diols, in the presence of a transesterification catalyst under conditions such that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols and one or more 1,1-diester-1-alkenes wherein the residue of the one or more diols and the one or more 1,1-diester-1 alkenes alternate along the chain 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.

16. A method according to claim 14 wherein the transesterification catalyst is one or more acids having a pKa in a polar aprotic solvent of about −

5 to about 14 or esters of the acids; and

is present in an amount of about 0.1 molar equivalents or less of the acid or the ester of acid per molar equivalent of the ester containing compounds transesterified;

and the method is performed at a temperature of about 20°

C. to about 160°

C.

15. A method comprising:

contacting one or more polyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more polyols having at least two of their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes; and

contacting the one or more multifunctional monomers one or more diols, one or more 1,1-diester 1-alkenes, and one or more dihydrocarbyl dicarboxylates in the presence of a transesterification catalyst under conditions that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols, one or more dihydrocarbyl dicarboxylates and one or more 1,1-diester-1-alkenes wherein the residues of each are disposed in a random manner along the chain 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.

17. A method according to claim 15 wherein the transesterification catalyst is a lipase enzyme catalyst and the transesterification step is performed at a temperature from about 20°

C. to about 70°

C.