Biodegradable polymers with pendant functional groups attached through amide bonds

Patent metadata

Field	Value
Publication number	US-9593201-B2
Application number	US-201314381295-A
Country	US
Kind code	B2
Filing date	Mar 1, 2013
Priority date	Mar 1, 2012
Publication date	Mar 14, 2017
Grant date	Mar 14, 2017

Abstract

Amide compounds are defined and are polymerized to create polyesters and polyurethanes having amide units bearing a pendant functional group, where the nitrogen atom of the amide group is part of the polymer backbone. The pendant functional group of the functionalized amide polymer may be modified or added by post polymerization functionalization of the functionalized amide polymer. The pendant functional group of the functionalized amide polymer may include a protecting group that may be removed after polymerization. The pendant functional groups of the functionalized amide polymers may be used to modulate the physical, chemical and biological properties of the polymers.

First claim

What is claimed is:

1. A functionalized amide polymer according to the following structure:

where every X c is a urethane group or every X c is an ester group; R 1 and R 2 may be the same or different and are each hydrocarbon groups; and where R 1 and R 2 may be selected to join to create a heterocyclic group that includes the nitrogen atom as a hetero atom within the heterocyclic group, R 4 is a hydrocarbon group, where the polymer includes at least one m unit and one n unit and m and n represent repeating units of the polymer in random or block configuration, M 1 and M 2 are pendant functional groups and M 2 is different from M 1 .

2. The functionalized amide polymer of claim 1 , where M 1 and M 2 are selected from the group consisting of organic pendant functional groups, amino acid side chains, and protected groups.

3. The functionalized amide polymer of claim 1 , where M 1 and M 2 are selected from the group consisting of imaging labels, peptides, and amino acids.

4. The functionalized amide polymer of claim 1 , where R 1 and R 2 are each ethylene groups.

5. A functionalized amide polymer comprising:
a polymer backbone selected from polyesters and polyurethanes;
a first amide group with a first pendant functional group, where the nitrogen atom of the first amide group is part of the polymer backbone, with the proviso that the pendant functional group is not a fatty oil; and
a second amide group with a pendant functional group different from the first pendant functional group, where the nitrogen atom of the second amide group is part of the polymer backbone.

6. The functionalized amide polymer of claim 5 , where the functionalized amide polymer includes a unit defined by formula (XV) or formula (XVI):

where each X c is a urethane group or an ester group; R 1 and R 2 may be the same or different and are each hydrocarbon groups; R 3 is a heterocyclic group that includes the nitrogen atom as a hetero atom within the heterocyclic group; y and z may be the same or different and are from 0 to 4, and M is a pendant functional group with the proviso that the pendant functional group is not a fatty oil.

7. The functionalized amide polymer of claim 5 , where the functionalized amide polymer includes a unit defined by formula (XVII) or formula (XVIII):

where each X c is a urethane group or an ester group; R 1 and R 2 may be the same or different and are each hydrocarbon groups; R 3 is a heterocyclic group that includes the nitrogen atom as a hetero atom within the heterocyclic group; y and z may be the same or different and are from 0 to 4, R 4 is a hydrocarbon group, and M is a pendant functional group with the proviso that the pendant functional group is not a fatty oil.

8. The functionalized amide polymer of claim 5 , wherein the polymer has a third amide group with a third pendant functional group, where the nitrogen atom of the amide group is part of the polymer backbone, and the third pendant functional group is different from the first and second functional group.

9. The functionalized amide polymer of claim 5 , wherein the polymer has a number average molecular weight (M n ) of at least 10,000 g/mol.

10. The functionalized amide polymer of claim 5 , where the first pendant functional group is selected from the group consisting of organic pendant functional groups, amino acid side chains, and protected groups.

11. The functionalized amide polymer of claim 10 , where the first pendant functional group is a group suitable for post polymerization functionalization and is selected from amines, hydroxyls, carboxylic acids, propargyls and azides.

12. The functionalized amide polymer of claim 5 , where the first pendant functional group is selected from the group consisting of imaging labels, peptides, and amino acids.

13. The functionalized amide polymer of claim 5 , where the first pendant functional group is a group defined by:

wherein x is from 0 to 6; and the second pendant functional group is an organic pendant functional group.

14. The functionalized amide polymer of claim 13 , wherein x is 2.

15. The functionalized amide polymer of claim 13 , where the first pendant group is a peptide and the second pendant functional group is a group defined by:
—(CH 2 ) x CONH(OC 2 H 5 ) x OCH 3

wherein each x is from 0 to 6.

16. The functionalized amide polymer of claim 15 , where the peptide is selected from the group consisting of GRGDS, RGD, and YIGSR.

17. The functionalized amide polymer of claim 10 , where the first pendant functional group is an amino acid side chain selected from histidine, alanine, isoleucine, arginine, leucine, asparagine, lysine, aspartic acid, methionine, cysteine, phenylalanine, glutamic acid, threonine, glutamine, tryptophan, glycine, valine, proline, serine, and tyrosine.

18. The functionalized amide polymer of claim 5 , where the functional amide polymer is a multifunctional polyester that includes the structure:

where every X c is an ester group; R 1 and R 2 are each ethylene groups; where the polymer includes at least one m unit and one n unit and m and n represent repeating units of the polymer in random or block configuration, and M 1 and M 2 are different pendant functional groups.

19. The functionalized amide polymer of claim 5 , where the functional amide polymer is a multifunctional amide polymer defined as:

where every X c is a urethane group or every X c is an ester group; R 1 and R 2 are each ethylene groups; R 4 is a hydrocarbon group, where the polymer includes at least one m unit and one n unit and m and n represent repeating units of the polymer in random or block configuration, and M 1 and M 2 are different pendant functional groups.

20. The functionalized amide polymer of claim 5 , where the functional amide polymer is a multifunctional polyurethane defined as:

wherein the polymer includes at least one m unit and one n unit and m and n represent repeating units of the polymer in random or block configuration, and M 1 and M 2 are different pendant functional groups.

21. The functionalized amide polymer of claim 5 , where the functional amide polymer is a multifunctional polyester defined as:

where the polymer includes at least one m unit and one n unit and m and n represent repeating units of the polymer in random or block configuration, and M 1 and M 2 are different pendant functional groups.

Assignees

• Univ Akron

Inventors

• Joy Abraham
• Gokhale Sachin
• Xu Ying

Classifications

• C08G63/6856 Primary

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08G18/3275

  containing two hydroxy groups · CPC title

• C08G63/916 Primary

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08G73/0233

  Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups · CPC title

• C08G18/73

  acyclic · CPC title