Bioelastomers and applications thereof

Patent metadata

Field	Value
Publication number	US-10106647-B2
Application number	US-201414916140-A
Country	US
Kind code	B2
Filing date	Sep 4, 2014
Priority date	Sep 5, 2013
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

In one aspect, compositions are described herein. In some embodiments, a composition described herein comprises the reaction product of (i) citric acid, a citrate, or an ester of citric acid with (ii) a polyol, and (iii) a monomer comprising one or more alkyne moieties and/or azide moieties. The reaction product, in some instances, comprises a polymer. Further, in some cases, a composition described herein comprises a plurality of polymers. In some embodiments, the polymers are selected to be reactive with one another through a click chemistry reaction scheme to form a polymer network. In another aspect, medical implants and medical devices are described herein, the implants and devices comprising a polymer or polymer network described herein.

First claim

That which is claimed is:

1. A composition comprising a polymer formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); and one or more monomers comprising one or more alkyne moieties and/or one or more azide moieties:

wherein
R 1 , R 2 , and R 3 are independently —H, —CH 3 , —CH 2 CH 3 , or M + ;
R 4 is —H;
R 5 is —H, —OH, —OCH 3 , —OCH 2 CH 3 , —CH 3 , —CH 2 CH 3 , —NH 2 , NHCH 3 , —CH 2 CH 2 NHCH 3 , —N(CH 3 ) 2 , or —CH 2 CH 2 N(CH 2 CH 3 ) 2 ;
R 6 is —H, —CH 3 , or —CH 2 CH 3 ,
R 7 is —H or —CH 3 ;
R 8 is —(CH 2 ) a , —(CH 2 CH 2 O) b —, or —(CH 2 OCH 2 ) b —;
R 9 is —H, —CH 3 , or a C2-C20 alkyl;
R 10 is —H, —C(O)CH 3 , or —C(O)CH 2 CH 3 ;
R 11 and R 12 are independently —OH or —NH 2 ;
M + is a monovalent cation;
X and Y are independently —O—or —NH—;
Z is —H or —CH 3 , or

a is an integer from 0 to 20;
b is an integer from 0 to 2000;
n is an integer between 1 and 2000; and
m and p are independently integers ranging from 1 to 20; and
wherein the monomer of Formula (B1) has at least one terminus comprising —OH or —NH 2 ; and
wherein, in the alternative, either:
(a) the one or more monomers comprising one or more azide moieties comprises a monomer of Formula (G1) or (G2):

wherein
R 20 is —CH 3 or —CH 2 CH 3 , or
(b) the one or more monomers comprising one or more alkyne moieties comprises a monomer of Formula (H1), (H2), (H3), (H4), (H5), or (H6):

wherein
R 20 is —CH 3 or —CH 2 CH 3 ; and
X is —NH—.

2. The composition of claim 1 , wherein one or more monomers of Formula (B1) are used and X is —O—.

3. The composition of claim 1 , wherein the one or more monomers comprising one or more alkyne and/or azide moieties comprises a polyol.

4. The composition of claim 1 , wherein the composition comprises a first polymer formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); and one or more monomers comprising one or more alkyne moieties; and a second polymer formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); and one or more monomers comprising one or more azide moieties.

5. The composition of claim 4 , wherein the composition comprises an azide-alkyne cycloaddition product.

6. The composition of claim 1 , wherein the polymer is formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); one or more monomers comprising one or more alkyne moieties and/or one or more azide moieties; and one or more monomers of Formula (C1), (C2), (C3), or (C4):

wherein p is an integer ranging from 1 to 10.

7. The composition of claim 1 , wherein the polymer is formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); one or more monomers comprising one or more alkyne moieties and/or one or more azide moieties; and one or more monomers of Formula (D1) or (D2):

wherein
R 13 is —H, —CH 3 , or —CH 2 CH 3 .

8. The composition of claim 1 , wherein the polymer is formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2) or (B3); one or more monomers comprising one or more alkyne moieties and/or one or more azide moieties; and one or more monomers of Formula (E):

wherein
R 14 is a side chain of an amino acid or an alkyl-substituted amino acid.

9. The composition of claim 1 , wherein the polymer is formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2) or (B3); one or more monomers comprising one or more alkyne moieties and/or one or more azide moieties; and one or more monomers of Formula (F):

wherein
R 15 , R 16 , R 17 , and R 18 are independently —H, —CH 2 (CH 2 ) x NH 2 , —CH 2 (CHR 19 )NH 2 , or —CH 2 (CH 2 )COOH;
R 19 is —COOH or —(CH 2 ) y COOH;
x is an integer ranging from 0 to 20; and
y is an integer ranging from 1 to 20.

10. The composition of claim 1 , wherein the one or more monomers comprising one or more azide moieties comprises a monomer of Formula (G1) or (G2).

11. The composition of claim 1 , wherein the one or more monomers comprising one or more alkyne moieties comprises a monomer of Formula (H1), (H2), (H3), (H4), (H5), or (H6).

12. The composition of claim 1 , further comprising a particulate inorganic material dispersed within a network formed by the polymer.

13. The composition of claim 12 , wherein the particulate inorganic material comprises hydroxyapatite.

14. The composition of claim 12 , wherein the particulate inorganic material is present in the polymer network in an amount up to about 70 weight percent, based on the total weight of the polymer network.

15. A core-shell polymeric scaffold comprising:
a core component having a first porosity; and
a shell component surrounding the core component and having a second porosity, the second porosity differing from the first porosity,
wherein the core component comprises a first polymer network formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); one or more monomers comprising an alkyne moiety; and one or more monomers comprising an azide moiety:

wherein
R 1 , R 2 , and R 3 are independently —H, —CH 3 , —CH 2 CH 3 , or M + ;
R 4 is —H;
R 5 is —H, —OH, —OCH 3 , —OCH 2 CH 3 , —CH 3 , —CH 2 CH 3 , —NH 2 , NHCH 3 , —CH 2 CH 2 NHCH 3 , —N(CH 3 ) 2 , or —CH 2 CH 2 N(CH 2 CH 3 ) 2 ;
R 6 is —H, —CH 3 , or —CH 2 CH 3 ,
R 7 is —H or —CH 3 ;
R 8 is —(CH 2 ) a—, —(CH 2 CH 2 O) b —, or —(CH 2 OCH 2 ) b— ;
R 9 is —H, —CH 3 , or a C2-C20 alkyl;
R 10 is —H, —C(O)CH 3 , or —C(O)CH 2 CH 3 ;
R 11 and R 12 are independently —OH or —NH 2 ;
M + is a monovalent cation;
X and Y are independently —O— or —NH—;
Z is —H, —CH 3 , or

a is an integer from 0 to 20;
b is an integer from 0 to 2000;
n is an integer between 1 and 2000; and
m and p are independently integers ranging from 1 to 20; and
wherein the monomer of Formula (B1) has at least one terminus comprising —OH or —NH2; and
wherein the shell component comprises a second polymer network formed from one or more monomers of Formula (A); one or more monomers of Formula (B1), (B2), or (B3); one or more monomers comprising an alkyne moiety; and one or more monomers comprising an azide moiety; and
wherein, in the alternative, either:
(a) the one or more monomers comprising one or more azide moieties comprises

Assignees

• Penn State Res Found

Inventors

• Yang Jian
• Guo Jinshan

Classifications

• A61L27/34

  Macromolecular materials · CPC title

• A61L2430/02

  for reconstruction of bones; weight-bearing implants · CPC title

• C08G18/68

  Unsaturated polyesters · CPC title

• A61L27/46

  with phosphorus-containing inorganic fillers · CPC title

• A61L2420/04

  Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases · CPC title