Polyhedral oligomeric silsesquioxane polyurethanes

Patent metadata

Field	Value
Publication number	US-9249254-B2
Application number	US-201113092331-A
Country	US
Kind code	B2
Filing date	Apr 22, 2011
Priority date	Apr 22, 2010
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

A multi-block thermoplastic polyurethanes system which incorporates polyhedral oligomeric silsesquioxane into conventional biodegradable thermoplastic polyurethanes built up by poly(ε-caproactone) and polyethylene glycol blocks, resulting in biostability. The multi-block thermoplastic polyurethanes are synthesized from lysine-diisocyanate with poly(ε-caprolactone)-diol, polyhedral oligomeric silsesquioxane-diol, and poly(ethylene glycol) using a one-step synthesis process.

First claim

What is claimed is:

1. A multiblock thermoplastic polyurethane, comprising:
a soft block including polyethylene glycol and poly(ε-caprolactone); and
a hard block including a diisocyanate and a polyhedral oligosilsesquioxane covalently tethered to said diisocyanate;
wherein the polyurethane comprises at least fifty percent polyethylene glycol; and
wherein the polyurethane has the formula [PEG 10k -DI] 50 -[PCL 1k -DI] 30 -[POSS-DI] 20 , where PEG 10k is polyethylene glycol with a molar mass of 10000, PCL 1k is poly(ε-caprolactone) with a molar mass of 1000, DI is a diisocyanate, and POSS is polyhedral oligomeric silsesquioxane.

2. The polyurethane of claim 1 , wherein said diisocyanate comprises lysine diisocyanate.

3. The polyurethane of claim 1 , wherein said polyhedral oligosilsesquioxane comprises 2,2,4-trimethyl-1,3-pentane polyhedral oligosilsesquioxane.

4. The polyurethane of claim 3 , wherein said multiblock thermoplastic polyurethane has the scheme:

5. A multiblock thermoplastic polyurethane, comprising:
a soft block including polyethylene glycol and poly(ε-caprolactone); and
a hard block including a diisocyanate and a polyhedral oligosilsesquioxane covalently tethered to said diisocyanate;
wherein the polyurethane comprises at least fifty percent polyethylene glycol; and
wherein said polyurethane has the formula [PEG 1k -DI] 50 -[PCL 1k -DI] 30 -[POSS-DI] 20 , where PEG 1k is polyethylene glycol with molar mass of 1000, PCL 1k is poly(ε-caprolactone) with a molar mass of 1000, DI is a diisocyanate, and POSS is polyhedral oligomeric silsesquioxane.

6. A method of forming a multiblock thermoplastic polyurethane, comprising the steps of:
dissolving poly(ε-caprolactone), polyethylene glycol, and a polyhedral oligosilsesquioxane diol in a solvent;
performing a nitrogen purge;
heating the dissolved poly(ε-caprolactone), polyethylene glycol and polyhedral oligosilsesquioxane;
adding a diisocyanate; and
adding a catalyst;
wherein the polyurethane comprises at least fifty percent polyethylene glycol; and
wherein said biostable polymer has the formula [PEG 10k -DI] 50 -[PCL 1k -DI] 30 -[POSS-DI] 20 , where PEG 10k is polyethylene glycol with a molar mass of 10000, of PCL 1k is poly(ε-caprolactone) with a molar mass of 1000, DI is a diisocyanate, and POSS is polyhedral oligomeric silsesquioxane.

7. The method of claim 6 , wherein said diisocyanate comprises lysine diisocyanate.

8. The method of claim 7 , wherein the catalyst is dibutyltin dilaurate.

9. The method of claim 8 , wherein the step of heating the dissolved poly(ε-caprolactone), polyethylene glycol, and polyhedral oligosilsesquioxane comprises heating to about 50 degrees Celsius under a nitrogen purge.

10. The method of claim 6 , further comprising the step of heating the dissolved poly(ε-caprolactone), polyethylene glycol and polyhedral oligosilsesquioxane and diisocyanate to 90 degrees Celsius after the step of adding said diisocyanate.

11. The method of claim 10 , further comprising the step of precipitating said multiblock thermoplastic polyurethane.

12. The method of claim 11 , wherein the step of precipitating said multiblock thermoplastic polyurethane comprises precipitating said polyurethane into an excess of n-hexane.

13. The method of claim 6 , wherein said multiblock thermoplastic polyurethane has the scheme:

14. A method of forming a multiblock thermoplastic polyurethane, comprising the steps of:
dissolving poly(ε-caprolactone), polyethylene glycol, and a polyhedral oligosilsesquioxane diol in a solvent;
performing a nitrogen purge;
heating the dissolved poly(ε-caprolactone), polyethylene glycol and polyhedral oligosilsesquioxane;
adding a diisocyanate; and
adding a catalyst;
wherein the polyurethane comprises at least fifty percent polyethylene glycol; and
wherein said biostable polymer has the formula [PEG 1k -DI] 50 -[PCL 1k -DI] 30 -[POSS-DI] 20 , where PEG 1k polyethylene glycol with a molar mass of 1000, PCL 1k is poly(ε-caprolactone) with a molar mass of 1000, DI is a diisocyanate, and POSS is polyhedral oligomeric silsesquioxane.

15. The polyurethane of claim 5 , wherein said diisocyanate comprises lysine diisocyanate.

16. The polyurethane of claim 15 , wherein said polyhedral oligosilsesquioxane comprises 2,2,4-trimethyl-1,3-pentane polyhedral oligosilsesquioxane.

17. The method of claim 14 , wherein said diisocyanate comprises lysine diisocyanate.

18. The method of claim 17 , wherein the catalyst is dibutyltin dilaurate.

19. The method of claim 18 , wherein the step of heating the dissolved poly(ε-caprolactone), polyethylene glycol, and polyhedral oligosilsesquioxane comprises heating to about 50 degrees Celsius under a nitrogen purge.

20. The method of claim 19 , further comprising the step of heating the dissolved poly(ε-caprolactone), polyethylene glycol and polyhedral oligosilsesquioxane and diisocyanate to 90 degrees Celsius after the step of adding said diisocyanate.

21. The method of claim 20 , further comprising the step of precipitating said multiblock thermoplastic polyurethane.

22. The method of claim 21 , wherein the step of precipitating said multiblock thermoplastic polyurethane comprises precipitating said polyurethane into an excess of n-hexane.

Assignees

• Mather Patrick
• Wu Jian
• Gu Xinzhu
• Univ Syracuse

Inventors

• Mather Patrick
• Wu Jian
• Gu Xinzhu

Classifications

• C08G18/4277

  Caprolactone and/or substituted caprolactone · CPC title

• C08G18/61

  Polysiloxanes · CPC title

• C08G18/4018

  Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48 · CPC title

• C08G18/4833

  Polyethers containing oxyethylene units · CPC title

• C08G18/3893

  containing silicon · CPC title