Thermal responsive polymer siloxanes, compositions, and method and applications related thereto

Patent metadata

Field	Value
Publication number	US-9259509-B2
Application number	US-201414286834-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	Apr 19, 2007
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

The invention relates to materials comprising siloxanes, preferably the materials have thermal-responsive properties. In some embodiments, the invention relates to silsesquioxane groups functionalized with polymers. In another embodiment, silsequioxane-polymer conjugates comprise polylactone segments. The silsequioxane-polymer conjugates may be crosslinked together to form a material, and these materials may be functionalized with bioactive compounds so that the materials have desirable biocompatibility or bioactivity when used in medical devices. In further embodiments, the invention relates to composite materials that contain a polymer matrix and aggregates, and in some embodiments, methods of making, and methods of using these materials. Preferably, the aggregates are calcium phosphate aggregates. Preferably, the material is resistant to fracture. In further embodiments, the materials are used in surgical procedures of bone replacement. In further embodiments, the materials contain polyhedral silsesquioxanes and/or biodegradable segments.

First claim

We claim:

1. A composition comprising:
a) a core comprising siloxane moieties;
b) at least three polymers grafted to said siloxane moieties to form a plurality of siloxane-polymer conjugates, wherein each of the said at least three polymers comprises at least two reactive functional groups selected from the group consisting of an ester group, an alkenyl group, a hydroxyl group, an amide group, and a carboxylic acid group;
c) a crosslinked network formed by linking groups joining two or more of said siloxane-polymer conjugates,
wherein
said siloxane moieties are caged structures,
said linking groups are selected from the group consisting of alkyl, aryl, polyethylene and urethane groups, and
said composition has a T g between 17° C. and 100° C.

2. The composition of claim 1 , wherein at least one of said at least three polymers is a polyester.

3. The composition of claim 1 , wherein said siloxane moieties are selected from the group consisting of silsesquioxanes and metallasiloxanes.

4. The composition of claim 3 , wherein said siloxane moieties are silsesquioxanes.

5. The composition of claim 1 , wherein said siloxane moieties are metallasiloxanes.

6. The composition of claim 5 , wherein said linking groups comprise aryl groups.

7. The composition of claim 5 , wherein said linking groups comprise alkyl groups.

8. The composition of claim 5 , wherein said linking groups comprise polyethylene groups.

9. The composition of claim 5 , wherein said linking groups comprises urethane groups.

10. The composition of claim 5 , wherein at least one of said at least three polymers is a polyester.

11. The composition of claim 5 , wherein said composition has one-way or two-way shape memory.

12. A method of supplementing or repairing a bone in a subject comprising:
1) providing
a) said composition of claim 1 , and
b) a subject suspected of or exhibiting symptoms associated with a bone disorder or dysfunction; and

2) administering said composition to said subject under conditions such said symptoms are reduced.

13. The method of claim 12 , wherein said mode of administration is surgical implantation.

14. The method of claim 12 , wherein the bone exhibiting said bone disorder or dysfunction is selected from the group consisting of cranial bones, mandible, ulna, humerus, radius, vertebrae, carpals, metacarpals, phalanges, ilium, ischium, pubis, femur, hip joint, patella, tibia, fibula, tarsals and metatarsals.

15. The method of claim 12 , wherein said bone disorder or dysfunction is selected from the group consisting of bone fracture, bone cyst, bone spur, bone tumor, craniosynostosis, fibrodysplasia ossificans progressiva, fibrous dysplasia, giant cell tumor of bone, hypophosphatasia, Klippel-Feil syndrome, metabolic bone disease, osteitis deformans, osteitis fibrosa cystica, osteitis pubis, condensing osteitis, osteitis condensans ilii, osteochondritis dissecans, osteochondroma, osteogenesis imperfecta, osteomalacia, osteomyelitis, osteopenia, osteopetrosis, osteoporosis, osteosarcoma, porotic hyperostosis, primary hyperparathyroidism and renal osteodystrophy.

16. The method of claim 12 , wherein said subject is a mammal.

17. The method of claim 12 , wherein at least one of said at least three polymers is a polyester.

18. The method of claim 12 , wherein said siloxane moieties are selected from the group consisting of silsesquioxanes and metallasiloxanes.

19. The method of claim 18 , wherein said siloxane moieties are silsesquioxanes.

20. The method of claim 18 , wherein said siloxane moieties are metallasiloxanes.

Assignees

• Univ Massachusetts Medical
• Univ Massachusetts

Inventors

• Song Jie
• Xu Jianwen

Classifications

• A61L27/18 Primary

  obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08G77/445

  containing polyester sequences · CPC title

• C08G77/045

  containing less than 25 silicon atoms · CPC title

• A61L31/06

  obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {(A61L31/041 takes precedence)} · CPC title

• C08G18/61

  Polysiloxanes · CPC title