Shape memory polymers

• US 10,526,437 B2
• Filed: 08/14/2017
• Issued: 01/07/2020
• 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:
  US15/676,740
• Publication Number:
  US 20170362372A1
• Time in Patent Office: 876 Days
• Field of Search: 524401
• 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 of preparing a crosslinked thermoset open cell shape memory polymer foam comprising:

forming the 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 includes isocyanate groups to match and react with hydroxyl groups of the at least one symmetric aliphatic hydroxyl containing monomer.

2. The method of claim 1 wherein:

the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof; and

the at least one symmetric aliphatic hydroxyl containing monomer includes at least one 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, hexamethylolmelamine, or combinations thereof.

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

1 ratio of the isocyanate groups to the hydroxyl 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 or the TEA is at least 1 to 1 and no more than 10 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 of claim 1 wherein the foam also comprises additives, the additives including at least one carbon nanotubes, exfoliated clay, particulate silica, glass fibers, carbon fibers, mineral fillers, metal fillers, glassy polymers, or liquid crystalline polymers, added to the polymer prior to foaming.

8. The method of claim 1 wherein the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof.

17. The method of claim 1 wherein:

the at least one aliphatic diisocyanate monomer includes hexamethylene diisocyanate (HDI); and

the at least one symmetric aliphatic hydroxyl containing monomer comprises at least one of N,N,N′

,N′

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

9. A method of preparing a crosslinked thermoset open cell shape memory polymer foam comprising:

forming the 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 includes isocyanate groups to match and react with hydroxyl groups of the at least one symmetric aliphatic hydroxyl containing monomer;

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

10. The method of claim 9 wherein:

the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof; and

the at least one symmetric aliphatic hydroxyl containing monomer includes at least one 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, hexamethylolmelamine, or combinations thereof.

11. The method of claim 9 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).

12. The method of claim 11 wherein a mole ratio of the HDI to at least one of the HPED or the TEA is at least 1 to 1 and no more than 10 to 1.

13. The method of claim 9 wherein the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof.

18. The method of claim 9 wherein:

the at least one aliphatic diisocyanate monomer includes hexamethylene diisocyanate (HDI); and

the at least one symmetric aliphatic hydroxyl containing monomer comprises at least one of N,N,N′

,N′

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

14. A method of preparing a crosslinked thermoset open cell polyurethane shape memory polymer foam comprising:

forming the crosslinked thermoset open cell polyurethane shape memory polymer foam, the 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 includes isocyanate groups to match and react with hydroxyl groups of the at least one symmetric aliphatic hydroxyl containing monomer.

15. The method of claim 14 wherein:

the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof; and

the at least one symmetric aliphatic hydroxyl containing monomer includes at least one 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, hexamethylolmelamine, or combinations thereof.

16. The method of claim 14 wherein the at least one aliphatic diisocyanate monomer includes at least one of octamethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, tetramethylene diisocyanate, trimethyl hexamethylene diisocyanate, trimethylene diisocyanate, ethylene diisocyanate, methylene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate, or combinations thereof.

19. The method of claim 14 wherein:

the at least one aliphatic diisocyanate monomer includes hexamethylene diisocyanate (HDI); and

the at least one symmetric aliphatic hydroxyl containing monomer comprises at least one of N,N,N′

,N′

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

20. The method of claim 14 wherein each of the hydroxyl groups matches with one of the isocyanate groups.