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

Patent metadata

Field	Value
Publication number	US-10087283-B2
Application number	US-201715472379-A
Country	US
Kind code	B2
Filing date	Mar 29, 2017
Priority date	Jun 3, 2016
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

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.

First claim

The invention claimed is:

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 3 or greater wherein the polyester macromers exhibit a number average molecular weight of about 600 to about 3000.

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

wherein Z is separately in each occurrence —R 2 OH or —R 1 ;
R 1 is separately in each occurrence a hydrocarbyl group which may contain one or more heteroatoms;
R 2 is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms wherein the hydrocarbylene group may contain one or more heteroatoms;
c is an integer of 1 or more; and
n is an integer of about 1 to 3.

4. A composition according to claim 2 wherein the one or more chains further comprise the residue of one or more dihydrocarbyl dicarboxylates.

5. A composition according to claim 4 wherein the polyol corresponds to the formula;

the 1,1-diester-1-alkenes correspond to the formula;

wherein the one or more dihydrocarbyl dicarboxylates correspond to the formula:

wherein R 1 is separately in each occurrence a hydrocarbyl group which may contain one or more heteroatoms;
R 2 is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms wherein the hydrocarbylene group may contain one or more heteroatoms;
R 3 is separately in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of the diester wherein the hydrocarbylene group may contain one or more heteroatoms; and
c is an integer of 1 or more.

6. 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 3 or greater wherein the number of repeating units in each chain is from 3 to 10.

7. A composition according to claim 6 wherein the number of repeating units in each chain is from 3 to 8.

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

9. A composition according to claim 1 wherein the polydispersity of the polyester macromers is about 1.05 to about 2.5.

10. A composition according to claim 1 wherein the polydispersity of the polyester macromers is about 1.05 to about 1.5.

11. A composition according to claim 4 wherein the ratio of the residue of 1,1-diestersubstituted-1-alkenes to the residue of dihydrocarbyl dicarboxylates is about 15:1 to about 1:1.

12. A composition according to claim 4 wherein the ratio of the residue of 1,1-diestersubstituted-1-alkenes to the residue of dihydrocarbyl dicarboxylates is about 10:1 to about 6:1.

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

14. A composition according to claim 3 wherein:
R 1 is separately in each occurrence alkyl, alkenyl, cycloalkyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or polyoxyalkylene, or both of the R 1 s form a 5-7 membered cyclic or heterocyclic ring; and
R 2 is separately in each occurrence alkylene, alkenylene, cycloalkylene, alkyl heterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, or polyoxyalkylene.

15. A composition according to claim 3 wherein:
R 1 is separately in each occurrence C 1-15 alkyl, C 2-15 alkenyl, C 3-9 cycloalkyl, C 2-20 heterocyclyl, C 6-18 aryl, C 7-25 alkaryl, C 7-25 aralkyl, C 5-18 heteroaryl or C 6-25 alkyl heteroaryl, or polyoxyalkylene, or both of the R 1 groups form a 5-7 membered cyclic or heterocyclic ring
R 2 is be 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 3 wherein:
R 1 is separately in each occurrence a C 1-4 alkyl.

17. A composition according to claim 5 wherein:
R 1 is separately in each occurrence alkyl, alkenyl, cycloalkyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or polyoxyalkylene, or both of the R 1 s form a 5-7 membered cyclic or heterocyclic ring;
R 2 is separately in each occurrence alkylene, alkenylene, cycloalkylene, heterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, or polyoxyalkylene;
wherein the recited groups of R 1 and R 2 may be substituted with one or more substituents.

18. A composition according to claim 5 wherein:
R 1 is separately in each occurrence C 1-15 alkyl, C 2-15 alkenyl, C 3-9 cycloalkyl, C 3-20 alkheterocyclyl, C 6-18 aryl, C 7-25 alkaryl, C 7-25 aralkyl, C 5-18 heteroaryl or C 6-25 alkyl heteroaryl, or polyoxyalkylene, or both of the R 1 groups form a 5-7 membered cyclic or heterocyclic ring
R 2 is separately in each occurrence a C 2-8 alkylene group;
R 3 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 R 1 and R 2 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 5 wherein:
R 1 is separately in each occurrence a C 1-4 alkyl, and,
R 3 is methylene.

Assignees

• Sirrus Inc

Inventors

• Palsule Aniruddha
• Sullivan Jeffrey M
• Parab Kshitij K
• King Elliott
• Barrett William

Classifications

• C08G63/52

  Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation · CPC title

• C08G63/60 Primary

  derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds · CPC title

• C08G63/87 Primary

  Non-metals or inter-compounds thereof (boron C08G63/84) · CPC title

• C07C69/593

  Dicarboxylic acid esters having only one carbon-to-carbon double bond · CPC title

• C08G63/16

  Dicarboxylic acids and dihydroxy compounds · CPC title