SHAPE MEMORY POLYMERS

• US 20170362372A1
• Filed: 08/14/2017
• Published: 12/21/2017
• 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.
• Granted Patent: US 10,526,437 B2
• Time in Patent Office: Days
• 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 for prostheses A61F2210/0014
• 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 method comprising:

forming a crosslinked thermoset open cell shape memory polymer foam from a crosslinked polyurethane polymer, the crosslinked polyurethane polymer comprising the reaction product of;

(a) at least one aliphatic diisocyanate monomer, and (b) at least one symmetric aliphatic hydroxyl containing monomer with a functionality greater than 2;

wherein the at least one aliphatic diisocyanate monomer and the at least one symmetric aliphatic hydroxyl containing monomer collectively provide matching isocyanate and hydroxyl groups to react with each other and minimize dangling chains in the foam.

2. The method of claim 1 wherein:

the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate; and

the at least one symmetric aliphatic hydroxyl containing monomer is selected from the group consisting of N,N,N′

,N′

Tetrakis (2-hydroxypropyl) ethylenediamine (HPED), triethanol amine (TEA), N,N,N′

,N′

-Tetrakis(2-hydroxyethyl) ethylenediamine (HEED), trimethylolpropane ethoxylate, glycerol, polycaprolactone triol, pentaerythritol, and hexamethylolmelamine.

3. The method of claim 1 wherein the at least one aliphatic diisocyanate monomer and the at least one symmetric aliphatic hydroxyl containing monomer collectively comprise a 1:

1 ratio of isocyanate to hydroxyl functional groups.

4. The method claim 1 wherein the at least one aliphatic diisocyanate monomer comprises hexamethylene diisocyanate (HDI) and the at least one symmetric aliphatic hydroxyl containing monomer comprises N,N,N′

,N′

-Tetrakis (2-hydroxypropyl) ethylenediamine (HPED) and triethanolamine (TEA).

5. The method of claim 4 wherein a mole ratio of the HDI to at least one of the HPED and the TEA is substantially 2 to 1.

6. The method of claim 1 wherein the at least one symmetric aliphatic hydroxyl containing monomer contains no ether linkages and no ester linkages.

7. The method claim 1 wherein the foam is dyed to promote adsorption of at least one wavelength of light.

8. The method of claim 7 wherein the foam is dyed with at least one of an indocyanine green based dye and a platinum based dye.

9. The method of claim 8 wherein the foam is included in an interventional medical device.

10. The method of claim 1 wherein the foam comprises additives selected from the group consisting of carbon nanotubes, exfoliated clay, particulate silica, glass fibers, carbon fibers, mineral fillers, metal fillers, glassy polymers, and liquid crystalline polymers added to the polymer prior to foaming.

11. The method of claim 10 wherein the additives comprise single walled carbon nanotubes.

12. The method of claim 1 wherein the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate.

13. A method comprising:

forming a crosslinked thermoset open cell shape memory polymer foam from a crosslinked polyurethane polymer, the crosslinked polyurethane polymer comprising the reaction product of;

(a) at least one aliphatic diisocyanate monomer, and (b) at least one symmetric aliphatic hydroxyl containing monomer with a functionality greater than 2;

wherein the at least one aliphatic diisocyanate monomer and the at least one symmetric aliphatic hydroxyl containing monomer collectively provide matching isocyanate and hydroxyl groups to react with each other and minimize dangling chains in the foam;

wherein the at least one symmetric aliphatic hydroxyl containing monomer includes polycaprolactone triol.

14. The method of claim 13 wherein:

the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate; and

the at least one symmetric aliphatic hydroxyl containing monomer includes an additional member selected from the group consisting of N,N,N′

,N′

Tetrakis (2-hydroxypropyl) ethylenediamine (HPED), triethanol amine (TEA), N,N,N′

,N′

-Tetrakis(2-hydroxyethyl) ethylenediamine (HEED), trimethylolpropane ethoxylate, glycerol, pentaerythritol, and hexamethylolmelamine.

15. The method of claim 13 wherein the at least one aliphatic diisocyanate monomer is hexamethylene diisocyanate (HDI) and the at least one symmetric aliphatic hydroxyl containing monomer further comprises N,N,N′

,N′

-Tetrakis (2-hydroxypropyl) ethylenediamine (HPED) and triethanolamine (TEA).

16. The method of claim 15 wherein a mole ratio of the HDI to at least one of the HPED and the TEA is substantially 2 to 1.

17. The method of claim 13 wherein the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate.

18. A method comprising:

forming a crosslinked thermoset open cell polyurethane shape memory polymer foam comprising the reaction product of;

(a) at least one aliphatic diisocyanate monomer, and (b) at least one symmetric aliphatic hydroxyl containing monomer with a functionality greater than 2;

wherein the at least one aliphatic diisocyanate monomer and the at least one symmetric aliphatic hydroxyl containing monomer collectively provide matching isocyanate and hydroxyl groups to react with each other and minimize dangling chains in the foam.

19. The method of claim 18 wherein:

the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate; and

the at least one symmetric aliphatic hydroxyl containing monomer is selected from the group consisting of N,N,N′

,N′

Tetrakis (2-hydroxypropyl) ethylenediamine (HPED), triethanol amine (TEA), N,N,N′

,N′

-Tetrakis(2-hydroxyethyl) ethylenediamine (HEED), trimethylolpropane ethoxylate, glycerol, polycaprolactone triol, pentaerythritol, and hexamethylolmelamine.

20. The method of claim 18 wherein the at least one aliphatic diisocyanate monomer is selected from the group consisting of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, and dicyclohexylmethane-4,4′

-diisocyanate.