Heteroatom containing cyclic dimers

• US 10,457,660 B2
• Filed: 03/05/2015
• Issued: 10/29/2019
• 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
• Primary Examiner(s): Jarrell, Noble E
• Assistant Examiner(s): Kenyon, John S
• Application Number:
  US14/639,668
• Publication Number:
  US 20150191444A1
• Time in Patent Office: 1,699 Days
• 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 composition comprising a polymer comprising a repeat unit of Formula (XX):

2. The composition polymer of claim 1, wherein R¹, R², R³, R⁴, and R⁵ are hydrogen;

n is from 1 to 10; and

R⁶ is C₁-C₆ alkyl.

5. The composition of claim 1, wherein the repeat unit comprises Formula (XXV):

6. The composition of claim 1, wherein the composition contains less than about 3% by weight of the monomer.

7. The composition of claim 1, wherein the polymer has a number average molecular weight of at least about 2000 Da, at least about 10,000 Da, at least about 100,000 Da, or at least about 1,000,000 Da.

8. The composition of claim 1, wherein the polymer hydrolyzes in an aqueous solution at a pH below about 5.0.

9. The composition of claim 1, wherein each repeat unit of the polymer has a configuration chosen from RR, RS, SR, and SS.

10. The composition of claim 1, further comprising a nutritive or pharmaceutical agent.

11. The composition of claim 1, further comprising at least one additional polymer.

12. The composition of claim 1, wherein the polymer comprises a first repeat unit comprising Formula (XX) and a second repeat unit.

13. The composition of claim 12, 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).

14. The composition of claim 12, wherein the second repeat unit is derived from a lactide, a lactone, a lactam, an hydroxyl alkanoate, or an hydroxyl ester.

3. A composition comprising a polymer comprising a repeat unit of Formula (XXa):

4. The composition of claim 3, wherein R², R³, R⁴, R⁵, R⁸ and R⁹ are hydrogen;

each of n and m is from 1 to 10; and

R⁶ and R¹⁰ are C₁-C₆ alkyl.

15. A process for forming a polymer comprising repeat units of Formula (XX), the process comprising contacting a plurality of compounds of Formula (II):

16. The process of claim 15, wherein the compounds of Formula (II) have Formula (V) and the repeat units of Formula (XX) have-Formula (XXV):

17. The process of claim 15, wherein the catalyst is tin(II) octanoate, aluminum(III) isopropoxide, zinc(II) lactate, an yttrium complex, a bis- or trisaryl tin complex, a heterobimetallic iron(II) complex, a titanium complex with bridged-biphenolate ligand, a cationic aluminum complex, or a pyridine catalyst;

and the reaction is conducted at a temperature from about 100°

C. to about 200°

C. under an inert atmosphere.

18. The process of claim 15, wherein the reaction is conducted in the presence of a ring opening initiator, the ring opening initiator being a small molecule or a polymer comprising at least one hydroxyl group and/or an amine group.

19. The process of claim 18, wherein the ring opening initiator is water, an alcohol, a polyol, a polyalkylene oxide, a glycol, a polyglycol, or a low molecular weight primary or secondary amine.

20. The process of claim 15, wherein the reaction is conducted in the presence of a solvent;

or the reaction is conducted in the absence of a solvent.

21. The process of claim 15, wherein the polymer comprising repeat units of Formula (XX) has a number average molecular weight of at least about 2,000 Da, at least about 10,000 Da, at least about 100,000 Da, or at least about 1,000,000 Da.

22. The process of claim 15, wherein the catalyst is tin(II) octanoate and the reaction is conducted at a temperature from about 120°

C. to about 180°

C. under an inert atmosphere.

23. The process of claim 22, wherein the reaction further comprise an alcohol as a ring opening initiator.

24. The process of claim 15, wherein the process further comprises contact with a plurality of additional monomers to form a copolymer comprising first repeat units of Formula (XX) and second repeat units derived from the additional monomers.

25. The process of claim 24, wherein the plurality of additional monomers is chosen from acrylates, aminoacrylates, alkylene succinates, alkylene oxalates, amides, amino acids, anhydrides, arylates, carbonates, cellulose, caprolactone, caprolactam, cyanoacrylates, cyclic ethers, dihydropyrans, dioxanes, dioxanones, ether ether ketones, ethylene glycol, fumarates, hydroxy alkanoates, hydroxy esters, imides, ketals, lactides, lactones, lactams, methacrylates, methyl olefins, orthoesters, phosphazines, styrenes, terephthalates, tetrafurans, trimethylene carbonate, urethanes, vinyl acetates, vinyl ketones, or vinyl halides.

26. The process of claim 25, wherein the additional monomers are lactides, lactones, lactams, hydroxy alkanoates, or hydroxy esters.

27. The process of claim 24, wherein the catalyst is tin(II) octanoate, aluminum(III) isopropoxide, zinc(II) lactate, an yttrium complex, a bis- or trisaryl tin complex, a heterobimetallic iron(II) complex, a titanium complex with bridged-biphenolate ligand, a cationic aluminum complex, or a pyridine catalyst;

and the reaction is conducted at a temperature from about 100°

C. to about 200°

C. under an inert atmosphere.

28. The process of claim 24, wherein the reaction is conducted in the presence of a ring opening initiator chosen from water, an alcohol, a polyol, a polyalkylene oxide, a glycol, a polyglycol, or a low molecular weight primary or secondary amine.

29. The process of claim 24, wherein the reaction is conducted in the presence of a solvent;

or the reaction is conducted in the absence of a solvent.

30. The process of claim 24, wherein the catalyst is tin(II) octanoate and the reaction is conducted at a temperature from about 120°

C. to about 180°

C. under an inert atmosphere.

31. The process of claim 30, wherein the reaction further comprises an alcohol as a ring opening initiator.