Hydrolysable linkers and cross-linkers for absorbable polymers

• US 9,045,396 B2
• Filed: 02/14/2014
• Issued: 06/02/2015
• Est. Priority Date: 09/17/2007
• Status: Active Grant

• Current Assignee: Bezwada Biomedical, LLC
• Original Assignee: Bezwada Biomedical, LLC
• Inventors: Bezwada, Rao S
• Primary Examiner(s): Valenrod, Yevegeny
• Assistant Examiner(s): Doletski, Blaine G
• Application Number:
  US14/180,561
• Publication Number:
  US 20140163253A1
• Time in Patent Office: 473 Days
• Field of Search: 560/45, 560/49
• US Class Current: 1/1
• CPC Class Codes: A47F 5/0006 Hangers for hanging articles on bars, tringles, bracket arms or the like dress holders, e.g. for clothing, shoes, A47G25/00; packages for hanging B65D; lockable clothing holders E05B69/00
• CPC Class Codes: A61L 17/00 Materials for surgical sutures or for ligaturing blood vessels surgical adhesives A61L24/00; surgical instruments, devices or methods for suturing or ligaturing A61B17/04, A61B17/12; supports or packages for suture materials A61B17/04; Materials for prostheses or catheters bone cements or surgical adhesives for soft body tissues A61L24/00; shape or structure of prostheses A61F2/00; shape or structure of catheters A61M5/00
• CPC Class Codes: A61L 17/105 Polyesters not covered by A61L17/12
• CPC Class Codes: A61L 17/12 Homopolymers or copolymers of glycolic acid or lactic acid
• CPC Class Codes: A61L 17/145 Coating
• CPC Class Codes: A61L 24/06 obtained by reactions only involving carbon-to-carbon unsaturated bonds A61L24/043, A61L24/046 take precedence
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 27/58 Materials at least partially resorbable by the body
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/145 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 31/148 Materials at least partially resorbable by the body
• CPC Class Codes: B65D 25/22 for facilitating lifting or suspending of containers
• CPC Class Codes: C07C 205/37 the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
• CPC Class Codes: C07C 205/43 to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
• CPC Class Codes: C07C 205/57 having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• CPC Class Codes: C07C 217/84 the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
• CPC Class Codes: C07C 219/34 having amino groups and esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
• CPC Class Codes: C07C 225/22 having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• CPC Class Codes: C07C 229/18 : the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 229/60 : with amino and carboxyl groups bound in meta- or para- positions
• CPC Class Codes: C07C 235/16 : having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C07C 265/12 : having isocyanate groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 69/34 : Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
• CPC Class Codes: C07C 69/67 : of saturated acids
• CPC Class Codes: C07C 69/708 : Ethers
• CPC Class Codes: C08G 63/16 : Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/916 : Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08L 67/04 : Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: Y02W 90/10 : Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
• CPC Class Codes: Y10T 24/44291 : including pivoted gripping member
• CPC Class Codes: Y10T 24/51 : Hanger on portable article support for manual attachment thereof to overhead support [e.g., drapery hook]
• CPC Class Codes: Y10T 428/139 : Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 442/10 : Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]

Abstract

The present invention relates to the discovery of new class of linear and multiarmed hydrolysable linkers and cross linkers for use in the synthesis of biodegradable polymers such as, polyesters, polyurethanes, polyamides, polyureas and degradable epoxy amine resin. The linear and multiarmed hydrolysable linkers of the present invention include symmetrical and/or unsymmetrical ether carboxylic acids, amines, amide diols, amine polyols and isocyanates.

Claims

1. A hydrolysable linker selected from a compound of formula X, XI, and XII:

2. The linker of claim 1, wherein:

R is a di-, tri, or tetra-radical derived from C_1-25 alkyl, aryl, or aryl-(C_1-6alkyl)_1-3-, wherein from 1-3 of the CH₂ groups, within the alkyl chain are optionally independently replaced by O atoms, such that each of said O atoms is attached only to carbon atoms in the alkyl chain, with the proviso that the O atoms are separated from the di-, tri, or tetra-radical chain ends by at least one carbon atom and that multiple O in the di-, tri, tetra-radical chain must be separated from each other by at least two carbon atoms;

provided that when R is a tri or tetra-radical, the 3^rd or 3^rd/4^th arms of formula X, XI, or XII are capped as shown for the 1^st and 2^nd arms in formula X, XI, or XIII, respectively;

each X is independently;

—

OC(═

O)CH₂—

, —

OC(═

O)CH(CH₃)—

, —

OC(═

O)CH₂OCH₂CH₂—

, or —

OC(═

O)CH₂CH₂CH₂CH₂CH₂—

;

each X¹ is independently;

—

CH₂C(═

O)O—

, —

CH(CH₃)C(═

O)O—

, —

CH₂CH₂OCH₂C(═

O)O—

, or —

CH₂CH₂CH₂CH₂CH₂C(═

O)O—

;

each Y is independently;

—

OCH₂C(═

O)—

, —

OCH(CH₃)C(═

O)—

, —

OCH₂CH₂OCH₂C(═

O)—

, or —

OCH₂CH₂CH₂CH₂CH₂C(═

O)—

;

each Y¹ is independently;

—

C(═

O)CH₂O—

, —

C(═

O)CH(CH₃)O—

, —

C(═

O)CH₂OCH₂CH₂O—

, or —

C(═

O)CH₂CH₂CH₂CH₂CH₂O—

.

3. The linker of claim 2, wherein:

R is a di-, tri, tetra-radical derived from C_1-25 alkyl, aryl, or aryl-(C_1-6alkyl)_1-3-, wherein from 1-3 of the CH₂ groups, within the alkyl chain are optionally independently replaced by O atoms, such that each of said O atoms is attached only to carbon atoms in the alkyl chain, with the proviso that the O atoms are separated from the di-, tri, or tetra-radical chain ends by at least one carbon atom and that multiple O in the di-, tri, or tetra-radical chain must be separated from each other by at least two carbon atoms;

provided that when R is a tri or tetra-radical, the 3^rd or 3^rd/4^th arms of formula X, XI, or XII are capped as shown for the 1^st and 2^nd arms in formula X, XI, or XIII, respectively;

each X is independently;

—

OC(═

O)CH₂—

or —

OC(═

O)CH(CH₃)—

;

each X¹ is independently;

—

CH₂C(═

O)O—

or —

CH(CH₃)C(═

O)O—

;

each Y is independently;

—

OCH₂C(═

O)—

or —

OCH(CH₃)C(═

O)—

; and

,

each Y¹ is independently;

—

C(═

O)CH₂O—

or —

C(═

O)CH(CH₃)O—

.

4. The linker of claim 1, wherein the linker is of Formula X.

5. The linker of claim 2, wherein the linker is of Formula X.

6. The linker of claim 3, wherein the linker is of Formula X.

7. The linker of claim 1, wherein the linker is of Formula XI.

8. The linker of claim 2, wherein the linker is of Formula XI.

9. The linker of claim 3, wherein the linker is of Formula XI.

10. The linker of claim 1, wherein the linker is of Formula XII.

11. The linker of claim 2, wherein the linker is of Formula XII.

12. The linker of claim 3, wherein the linker is of Formula XII.

13. The linker of claim 1, wherein the linker is of formula X and is selected from:

14. The linker of claim 1, wherein the linker is of formula XI and is selected from:

15. The linker of claim 1, wherein the linker is of formula XII and is selected from:

16. The linker of claim 1, wherein the linker is of formula XII and is:

17. The linker of claim 1, wherein the linker is of formula XII and is:

18. The linker of claim 1, wherein the linker is of formula XII and is:

19. The linker of claim 1, wherein the linker is of formula XII and is:

20. The linker of claim 1, wherein the linker is of formula XII and is:

21. The linker of claim 1, wherein the linker is of formula XII and is:

22. The linker of claim 1, wherein the linker is of formula XII and is: