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

• US 9,745,413 B1
• Filed: 02/20/2017
• Issued: 08/29/2017
• 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, Sullivan, Jeffrey M., Parab, Kshitij K., King, Elliott, Barrett, William
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/437,164
• Time in Patent Office: 190 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 a polyester macromer containing one or more chains of repeating units comprising 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 wherein the number of repeating units in each chain is 2 or greater;

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 one or more chains or the polyester macromer further comprise the residue of one or more dihydrocarbyl dicarboxylates, and wherein the polyol corresponds to the formula;

5. A composition according to claim 1 wherein the number of repeating units in each chain is from 2 to 10.

6. A composition according to claim 1 wherein the number of repeating units in each chain is from 2 to 8.

7. A composition according to claim 1 wherein the number of repeating units in each chain is from 3 to 6.

13. A composition according to claim 1 wherein the polyester macromers exhibit a number average molecular weight of about 600 to about 2000.

17. A composition according to claim 3 wherein:

R¹ is separately in each occurrence alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroaryl, or polyoxyalkylene, or both of the R¹s form a 5-7 membered cyclic or heterocyclic ring;

R² is separately in each occurrence alkylene, alkenylene, cycloalkylene, arylene, aralkylene, alkarylene, heteroarylene, or polyoxyalkylene;

wherein the recited groups of R¹ and R² may be substituted with one or more substituents.

18. A composition according to claim 3 wherein:

R¹ is separately in each occurrence C_1-15 alkyl, C_2-15 alkenyl, C_3-9 cycloalkyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or polyoxyalkylene, or both of the R¹ groups form a 5-7 membered cyclic or heterocyclic ring

R² is separately in each occurrence a C_2-8 alkylene group;

R³ is separately in each occurrence C_8-14 arylene, C_8-12 cycloalkylene, C_1-12 alkylene or C_2-12 alkenylene;

wherein the recited groups of R¹ and R² may be substituted with one or more halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester groups.

19. A composition according to claim 3 wherein:

R¹ is separately in each occurrence a C_1-4 alkyl, and,

R³ is methylene.

2. A composition comprising a polyester macromer containing one or more chains of repeating units comprising 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 wherein the number of repeating units in each chain is 2 or greater;

wherein the one or more chains of the polyester macromer further comprise the residue of one or more dihydrocarbyl dicarboxylates.

4. A composition according to claim 2 wherein the polyester macromers exhibit a number average molecular weight of about 600 to about 3000.

11. A composition according to claim 2 wherein the ratio of the residue of 1,1-diester substituted-1-alkenes to the residue of dihydrocarbyl dicarboxylates is about 15:

1 to about 1;

1.

12. A composition according to claim 2 wherein the ratio of the residue of 1,1-diester substituted-1-alkenes to the residue of dihydrocarbyl dicarboxylates is about 10:

1 to about 6;

1.

8. A composition comprising a polyester macromer containing one or more chains of repeating units comprising 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 wherein the number of repeating units in each chain is 2 or greater;

wherein the polydispersity of the polyester macromers is about 1.05 to about 2.5.

9. A composition according to claim 8 wherein the polyester macromer corresponds to Formula 1

10. A composition according to claim 8 wherein the polydispersity of the polyester macromers is about 1.05 to about 1.5.

14. A composition according to claim 9 wherein:

R¹ is separately in each occurrence alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroaryl, polyoxyalkylene, or both of the R¹s form a 5-7 membered cyclic or heterocyclic ring; and

R² is separately in each occurrence alkylene, alkenylene, cycloalkylene, arylene, aralkylene, alkarylene, or polyoxyalkylene.

15. A composition according to claim 9 wherein:

R¹ is separately in each occurrence C_1-15 alkyl, C_2-15 alkenyl, C_3-9 cycloalkyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or polyoxyalkylene, or both of the R¹ groups form a 5-7 membered cyclic or heterocyclic ring

R² is separately in each occurrence a C_2-8 alkylene group;

wherein the recited groups may be substituted with one or more halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester groups.

16. A composition according to claim 9 wherein:

R¹ is separately in each occurrence a C_1-4 alkyl.