Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments

Abstract

Thermoplastic polyurethanes having an alternating sequence of hard and soft segments in which a nanostructured polyhedral oligosilsesquioxane diol is used as a chain extender to form a crystalline hard segment constituting SMPs. The polyurethanes are formed by reacting a polyol, a chain extender dihydroxyl-terminated polyhedral oligosilsesquioxane and a diisocyanate. The polyurethanes have multiple applications including for example, implants for human health care, drug delivery matrices, superabsorbant hydrogels, coatings, adhesives, temperature and moisture sensors, etc.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS[0001]This application is a continuation of U.S. Nonprovisional patent application Ser. No. 11 / 111,388 filed Apr. 21, 2005, which is a continuation-in-part application of U.S. Nonprovisional patent application Ser. No. 10 / 683,167 filed Oct. 10, 2003 and issued Aug. 15, 2006 as U.S. Pat. No. 7,091,297 B2, which claims benefit of U.S. Provisional Application Nos. 60 / 418,023 filed Oct. 11, 2002, 60 / 466,401 filed Apr. 29, 2003, 60 / 419,506 filed Oct. 18, 2002, 60 / 488,590 filed Jul. 18, 2003, and 60 / 488,323 filed Jul. 18, 2003; each of which is incorporated herein by reference in its entirety. U.S. Nonprovisional patent application Ser. No. 10 / 425,451 filed Apr. 29, 2003, and U.S. Provisional Patent Application No. 60 / 377,544 filed May 2, 2008, to which it claims priority, are also incorporated herein by reference.TECHNICAL FIELD[0002]The instant disclosure relates to shape memory polymers and more particularly thermoplastic polyurethanes with an alt...

AI Technical Summary

Benefits of technology

[0009]It is another object of the invention to provide hybrid polyurethane SMPs evidencing sharp and tunable transition temperatures, adjustable stiffness above their transition temperatures, especially physical properties at 37° C. controlled by the level of POSS content, and thermal processability above the melting point of the POSS domains.

[0010]It is yet another object of the invention to provide hybrid polyurethane SMPs which possess excellent shape recovery effect at the recovery temperature and the retracting force is adjustable according to the composition of the POSS.

[0031]Any of the hybrid polyurethane polymers mentioned above may be filled with, for example, nanoparticles of boron nitride, silica, titanium dioxide, montmorillonite, clay, Kevlar, staple, aluminum nitride, barium subcarbonate and bismuth subcarbonate. Clay and silica can be used to, for example, increase the modulus of the plastic. Dispersing agents and / or compatibilizing agents may be used, for example, to improve the blending of polymers and the blending of polymers with fillers. Dispersing agents and / or compatibilizing agents include, for example, ACRAWAX® (ethylene bis-stearamide), polyurethanes and ELVALOY® (acrylic functionalized polyethylene).

[0032]In one embodiment, the rate of biodegradation of the thermoplastic polyurethane shape memory polymer can be controlled by adjusting the content of POSS chain extender, the content and composition of the polyol. For example, the biodegradation rate can be a) decreased by increasing the amount of POSS chain extender in the polymer; b) decreased by increasing the molecular weight of the polyol in the polymer; or c) increased by increasing the amount of hydrolysable groups in the polyol.

Problems solved by technology

The use of chemical crosslinking in both of these cases limits the types of processing possible and forever sets the equilibrium shape at the point of network formation.

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