Shape memory polymers

• US 9,051,411 B2
• Filed: 10/15/2010
• Issued: 06/09/2015
• Est. Priority Date: 08/16/2004
• Status: Active Grant

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Inventors: Wilson, Thomas S., Bearinger, Jane P.
• Primary Examiner(s): PAK, HANNAH J
• Application Number:
  US12/905,949
• Publication Number:
  US 20110039967A1
• Time in Patent Office: 1,698 Days
• Field of Search: 524/105, 524/590, 524/401, 528/44, 528/68, 528/85, 521/164, 521/170
• US Class Current: 1/1
• CPC Class Codes: A61B 17/3498 Valves therefor, e.g. flapper valves, slide valves haemostasis valves A61M39/06; check valves A61M39/24
• CPC Class Codes: A61B 2017/00867 shape memory effect
• CPC Class Codes: A61B 2017/00871 polymeric
• CPC Class Codes: A61B 2017/2932 Transmission of forces to jaw members
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 18/08 Processes
• CPC Class Codes: C08G 18/3203 Polyhydroxy compounds
• CPC Class Codes: C08G 18/3221 hydroxylated esters of carboxylic acids other than higher fatty acids
• CPC Class Codes: C08G 18/3271 Hydroxyamines
• CPC Class Codes: C08G 18/3281 containing three hydroxy groups
• CPC Class Codes: C08G 18/3284 containing four hydroxy groups
• CPC Class Codes: C08G 18/3287 containing cycloaliphatic groups
• CPC Class Codes: C08G 18/3851 containing three nitrogen atoms in the ring
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 2280/00 Compositions for creating shape memory
• CPC Class Codes: C08J 9/0085 Use of fibrous compounding ingredients C08J9/0076 takes precedence
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 75/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: C08L 75/14 Polyurethanes having carbon-to-carbon unsaturated bonds

Abstract

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Claims

1. A crosslinked thermoset shape memory polyurethane polymer medical device comprising:

a crosslinked thermoset polyurethane polymer comprising a covalently bonded network structure and a reaction product of an aliphatic diisocyanate monomer reacted with at least one symmetric hydroxyl containing monomer;

wherein said polymer has shape memory behavior and is formed into a permanent primary shape, re-formed into a stable secondary shape, and is configured to be controllably actuated to recover said permanent primary shape;

wherein the diisocyanate monomer and the at least one symmetric hydroxyl containing monomer are formulated to a 1;

1 ratio of isocyanate to hydroxyl functional groups;

wherein the at least one symmetric hydroxyl containing monomer includes at least one of N,N,N′

,N′

-tetrakis (2-hydroxypropyl) ethylenediamine (HPED) and triethanol amine (TEA);

wherein the polymer has a Young'"'"'s modulus in a range of 1 to 100 MPa at a temperature above a glass transition temperature of the polymer.

2. The device of claim 1:

wherein the diisocyanate monomer includes hexamethylene diisocyanate (HDI), and the at least one symmetric hydroxyl containing monomer includes HPED and TEA.

3. The device of claim 1 wherein the diisocyanate monomer is hexamethylene diisocyanate (HDI) and the at least one symmetric hydroxyl containing monomer is HPED.

4. The device of claim 3 wherein the mole ratio of HDI to HPED is 2 to 1.

5. The device of claim 1, wherein the polymer has biocompatibility and biostability and the diisocyanate monomer contains no ether or ester linkages.

6. The device of claim 1 wherein the polymer is dyed.

7. The device of claim 3 wherein the polymer is dyed with indocyanine green or platinum based dyes.

8. The device of claim 1 wherein the diisocyanate monomer is symmetric.

9. The device of claim 2 wherein the polymer also contains additional material selected from the group consisting of carbon nanotubes, exfoliated clay, glass fibers, carbon fibers, mineral fillers, metal fillers, glassy polymers, and liquid crystalline polymers.

10. The device of claim 9 wherein the additional material includes glassy polymers whose refractive index is matched to that of the polymer to which the additional material is added in order to minimize light scattering.

11. The device of claim 1 wherein the diisocyanate monomer and the at least one symmetric hydroxyl containing monomer are selected to minimize dangling chains.

12. The device of claim 2 wherein the diisocyanate monomer is symmetric in structure.

13. The device of claim 2 wherein the HDI composes between 53.9-61.0 weight % of the polymer, the HPED composes between 10.8-47 weight % of the polymer, and the TEA composes 0-28.2 weight % of the polymer.