HETEROATOM CONTAINING CYCLIC DIMERS

• US 20150191444A1
• Filed: 03/05/2015
• Published: 07/09/2015
• Est. Priority Date: 02/09/2012
• Status: Active Grant

• Current Assignee: Novus International, Inc. (Nippon Soda Company Limited)
• Original Assignee: Novus International, Inc. (Nippon Soda Company Limited)
• Inventors: Arhancet, Graciela B., Mahoney, Matthew, Wang, Xiaojun
• Granted Patent: US 10,457,660 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: A23K 20/10 Organic substances
• CPC Class Codes: A23K 50/10 for ruminants
• CPC Class Codes: A23K 50/75 for poultry
• CPC Class Codes: C07D 265/33 Two oxygen atoms, in positions 3 and 5
• CPC Class Codes: C07D 319/12 not condensed with other rings
• CPC Class Codes: C08G 63/6882 derived from hydroxy carboxylic acids
• CPC Class Codes: C08G 63/85 Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof C08G63/823 takes precedence
• CPC Class Codes: C08G 67/00 Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
• CPC Class Codes: C08G 75/02 Polythioethers
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence

Abstract

The present invention provides cyclic dimers of alpha acids and polymers derived therefrom. Also provided are processes for preparing and methods of using the cyclic dimers and the polymers derived from the cyclic dimers.

Claims

1. A process for preparing a compound comprising Formula (IX), the process comprising (a) contacting a compound comprising Formula (VI) with a compound comprising Formula (VII) or a compound comprising Formula (VIII) and an acid catalyst and (b) dehydrating the resulting reaction mixture to form the compound comprising Formula (IX), the compounds comprising Formula (IX), (VI), (VII), and (VIII):

2. The process of claim 1, wherein the acid catalyst is p-toluene sulfonic acid;

the reaction mixture is heated to a temperature from about 100°

C. to about 150°

C.; and

the reaction mixture is dehydrated by distillation.

3. The process of claim 1, wherein the compound comprising Formula (VI) and the compound comprising Formula (VIII) both comprise Formula (VIb) and the compound comprising Formula (IX) comprises Formula (V):

4. The process of claim 1, wherein the compound comprising Formula (IX) is isolated as a substantially pure isomer, the isomer having a configuration at ring atoms 3 and 6 chosen from RR, RS, SR, and SS, respectively.

5. A process for preparing a compound comprising Formula (IX), the process comprising (a) heating a compound comprising Formula (VI) with a compound comprising Formula (VII) or a compound comprising Formula (VIII) to form a polymer and (b) heating the polymer at a temperature of about 200°

C. and a pressure of less than about 1 Torr to form the compound comprising Formula (IX), the compounds comprising Formula (IX), (VI), (VII), and (VIII);

6. The process of claim 5, wherein the compound comprising Formula (VI) and the compound comprising Formula (VIII) both comprise Formula (VIb) and the compound comprising Formula (IX) comprises Formula (V):

7. The process of claim 5, wherein step (a) is conducted at a temperature from about 100°

C. to about 150°

C.

8. The process of claim 5, wherein the compound comprising Formula (IX) is isolated as a substantially pure isomer, the isomer having a configuration at ring atoms 3 and 6 chosen from RR, RS, SR, and SS, respectively.

9. A polymer comprising a repeat unit comprising Formula (XX):

10. The polymer of claim 9, wherein R¹, R², R³, R⁴, and R⁵ are hydrogen;

n is from 1 to 10;

Z is chosen from sulfur, sulfone, sulfoxide, and selenium;

R⁶ is lower chain alkyl, and R⁷, if present, is hydrogen or lower chain alkyl.

11. The polymer of claim 9, wherein the repeat unit comprises Formula (XXa):

12. The polymer of claim 9, wherein R², R³, R⁴, R⁵, R⁸ and R⁹ are hydrogen;

each of n and m is from 1 to 10;

Y and Z are independently chosen from sulfur, sulfone, sulfoxide, and selenium;

R⁶ and R¹⁰ are lower chain alkyl; and

R⁷ and R¹¹, if present, are independently hydrogen or lower chain alkyl.

13. The polymer of claim 9, wherein the repeat unit comprises Formula (XXV):

14. The polymer of claim 9, wherein the polymer is substantially free of a monomer.

15. The polymer of claim 9, wherein the average molecular weight of the polymer is at least about 10,000 Da, at least about 100,000 Da, or at least about 1,000,000 Da.

16. The polymer of claim 9, wherein the polymer hydrolyzes in an aqueous solution at a pH below about 5.0.

17. The polymer of claim 9, wherein each repeat unit of the polymer has a configuration chosen from RR, RS, SR, and SS.

18. The polymer of claim 9, wherein the polymer is used as a plasticizer, adhesive, coating, lacquer, film, emulsifier, antioxidant, antimicrobial agent, anticorrosive agent, feed composition, packaging material, consumer product, medical application, or agricultural application.

19. A composition comprising the polymer of claim 9 and a nutritive or pharmaceutical agent.

20. A composition comprising the polymer of claim 9 and at least one additional polymer.

21. The polymer of claim 9, wherein the polymer comprise a first repeat unit comprising Formula (XX) and at least one second repeat unit.

22. The polymer of claim 21, wherein the second repeat unit comprises Formula (XX), provided the second repeat unit is substituted differently in at least one position than the first repeat unit comprising Formula (XX).

23. The polymer of claim 22, wherein the second repeat unit is chosen from a lactide, a lactone, a lactam, an hydroxyl alkanoate, an hydroxyl ester, a cyclic ether, a tetrahydrofuran, a dioxane, a dioxanone, and mixtures thereof.

24. A polymer comprising Formula (XXI)

25. The polymer of claim 24, wherein the polymer comprises Formula (XXVI):

26. The polymer of claim 24, wherein X is oxygen and R is alkyl.

27. A process for forming a polymer, the process comprising contacting a plurality of compounds comprising Formula (II):

28. The process of claim 27, wherein the compound comprises Formula (V) and the repeat unit comprises Formula (XXV):

29. The process of claim 27, wherein the catalyst is tin(II) octanoate and the process is conducted at a temperature from about 120°

C. to about 180°

C. under an inert atmosphere.

30. The process of claim 27, wherein the process produces a polymer having an average molecular weight of at least about 10,000 Da, at least about 100,000 Da, or at least about 1,000,000 Da.

31. The process of claim 27, wherein the process further comprises contact with at least one additional monomer to form a copolymer.

32. The process of claim 31, wherein the additional monomer is chosen from a lactide, a lactone, a lactam, a hydroxyalkanoate, a hydroxyester, a cyclic ether, a tetrahydrofuran, a dioxane, a dioxanone, and mixtures thereof.