A Processable Shape Memory Polymer System for Biomedical Applications

Hearon, Keith; Wierzbicki, Mark A.; Nash, Landon D.; Landsman, Todd L.; Laramy, Christine; Lonnecker, Alexander T.; Gibbons, Michael C.; Ur, Sarah; Cardinal, Kristen O.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

doi:10.1002/adhm.201500156

A Processable Shape Memory Polymer System for Biomedical Applications

Journal Article · Thu Apr 30 00:00:00 EDT 2015 · Advanced Healthcare Materials

DOI:https://doi.org/10.1002/adhm.201500156· OSTI ID:1828129

Hearon, Keith ^[1]; Wierzbicki, Mark A. ^[1]; Nash, Landon D. ^[1]; Landsman, Todd L. ^[1]; Laramy, Christine ^[1]; Lonnecker, Alexander T. ^[1]; Gibbons, Michael C. ^[2]; Ur, Sarah ^[2]; Cardinal, Kristen O. ^[2]; Wilson, Thomas S. ^[3]; Wooley, Karen L. ^[1]; Maitland, Duncan J. ^[1]

Texas A & M Univ., College Station, TX (United States)
California Polytechnic State Univ. (CalPoly), San Luis Obispo, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities are synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature (T_g) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene “click” reactions to achieve postpolymerization crosslinking. Polyurethanes containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105 °C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ m^–3 at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); National Institutes of Health (NIH)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1828129

Report Number(s):: LLNL-JRNL--828368; 1043766

Journal Information:: Advanced Healthcare Materials, Journal Name: Advanced Healthcare Materials Journal Issue: 9 Vol. 4; ISSN 2192-2640

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (22)

Thiol-Ene Click Chemistry Hoyle, Charles E.; Bowman, Christopher N. Angewandte Chemie International Edition, Vol. 49, Issue 9, p. 1540-1573 https://doi.org/10.1002/anie.200903924	journal	February 2010
Shape memory polymers based on uniform aliphatic urethane networks Wilson, T. S.; Bearinger, J. P.; Herberg, J. L. Journal of Applied Polymer Science, Vol. 106, Issue 1, p. 540-551 https://doi.org/10.1002/app.26593	journal	January 2007
Post-polymerization crosslinked polyurethane shape memory polymers Hearon, Keith; Gall, Ken; Ware, Taylor Journal of Applied Polymer Science, Vol. 121, Issue 1, p. 144-153 https://doi.org/10.1002/app.33428	journal	February 2011
In vivo response to an implanted shape memory polyurethane foam in a porcine aneurysm model Rodriguez, Jennifer N.; Clubb, Fred J.; Wilson, Thomas S. Journal of Biomedical Materials Research Part A, Vol. 102, Issue 5, p. 1231-1242 https://doi.org/10.1002/jbm.a.34782	journal	May 2013
Photothermal properties of shape memory polymer micro-actuators for treating stroke Maitland, Duncan J.; Metzger, Melodie F.; Schumann, Daniel Lasers in Surgery and Medicine, Vol. 30, Issue 1 https://doi.org/10.1002/lsm.10007	journal	January 2002
Recent Trends in the Chemistry of Shape-Memory Polymers Julich-Gruner, Konstanze K.; Löwenberg, Candy; Neffe, Axel T. Macromolecular Chemistry and Physics, Vol. 214, Issue 5 https://doi.org/10.1002/macp.201200607	journal	December 2012
Three-Dimensional Flexible Electronics Enabled by Shape Memory Polymer Substrates for Responsive Neural Interfaces Ware, Taylor; Simon, Dustin; Hearon, Keith Macromolecular Materials and Engineering, Vol. 297, Issue 12 https://doi.org/10.1002/mame.201200241	journal	November 2012
Evaluation of fracture toughness and mechanical properties of ternary thiol–ene–methacrylate systems as resin matrix for dental restorative composites Beigi, Saeed; Yeganeh, Hamid; Atai, Mohammad Dental Materials, Vol. 29, Issue 7 https://doi.org/10.1016/j.dental.2013.04.015	journal	July 2013
Novel waterborne UV-crosslinkable thiol–ene polyurethane dispersions: Synthesis and film formation Otts, Daniel B.; Heidenreich, Erik; Urban, Marek W. Polymer, Vol. 46, Issue 19 https://doi.org/10.1016/j.polymer.2005.06.075	journal	September 2005
Effect of chemical structure and crosslinking density on the thermo-mechanical properties and toughness of (meth)acrylate shape memory polymer networks Safranski, David L.; Gall, Ken Polymer, Vol. 49, Issue 20 https://doi.org/10.1016/j.polymer.2008.07.060	journal	September 2008
Newly UV-curable polyurethane coatings prepared by multifunctional thiol- and ene-terminated polyurethane aqueous dispersions mixtures: Preparation and characterization Yang, Zhenglong; Wicks, Douglas A.; Hoyle, Charles E. Polymer, Vol. 50, Issue 7 https://doi.org/10.1016/j.polymer.2008.12.018	journal	March 2009
Synthesis and thermomechanical behavior of (qua)ternary thiol-ene(/acrylate) copolymers Kasprzak, Scott E.; Martin, Blanton; Raj, Tulika Polymer, Vol. 50, Issue 23 https://doi.org/10.1016/j.polymer.2009.09.044	journal	November 2009
Photopolymerized thiol-ene systems as shape memory polymers Nair, Devatha P.; Cramer, Neil B.; Scott, Timothy F. Polymer, Vol. 51, Issue 19 https://doi.org/10.1016/j.polymer.2010.07.027	journal	September 2010
UV curable glycidyl carbamate based resins Harkal, Umesh D.; Muehlberg, Andrew J.; Webster, Dean C. Progress in Organic Coatings, Vol. 73, Issue 1 https://doi.org/10.1016/j.porgcoat.2011.08.014	journal	January 2012
The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers Hearon, Keith; Smith, Sarah E.; Maher, Cameron A. Radiation Physics and Chemistry, Vol. 83 https://doi.org/10.1016/j.radphyschem.2012.10.007	journal	February 2013
A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T. Macromolecules, Vol. 46, Issue 22 https://doi.org/10.1021/ma4018372	journal	November 2013
Comparison of Small Molecule and Polymeric Urethanes, Thiourethanes, and Dithiourethanes: Hydrogen Bonding and Thermal, Physical, and Mechanical Properties Li, Qin; Zhou, Hui; Wicks, Douglas A. Macromolecules, Vol. 42, Issue 6 https://doi.org/10.1021/ma802848t	journal	February 2009
Review of progress in shape-memory polymers Liu, C.; Qin, H.; Mather, P. T. Journal of Materials Chemistry, Vol. 17, Issue 16 https://doi.org/10.1039/b615954k	journal	January 2007
Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis Hoyle, Charles E.; Lowe, Andrew B.; Bowman, Christopher N. Chemical Society Reviews, Vol. 39, Issue 4 https://doi.org/10.1039/b901979k	journal	January 2010
Biomedical applications of thermally activated shape memory polymers Small, IV, Ward; Singhal, Pooja; Wilson, Thomas S. Journal of Materials Chemistry, Vol. 20, Issue 17, p. 3356-3366 https://doi.org/10.1039/b923717h	journal	January 2010
Porous Shape-Memory Polymers Hearon, Keith; Singhal, Pooja; Horn, John Polymer Reviews, Vol. 53, Issue 1 https://doi.org/10.1080/15583724.2012.751399	journal	January 2013
Mechanical Requirements of Shape-Memory Polymers in Biomedical Devices Safranski, David L.; Smith, Kathryn E.; Gall, Ken Polymer Reviews, Vol. 53, Issue 1 https://doi.org/10.1080/15583724.2012.752385	journal	January 2013

Cited By (14)

Poly(ethylene glycol)-sheddable reduction-sensitive polyurethane micelles for triggered intracellular drug delivery for osteosarcoma treatment Yang, Zhengjie; Guo, Qianping; Cai, Yan Journal of Orthopaedic Translation, Vol. 21 https://doi.org/10.1016/j.jot.2019.11.001	journal	March 2020
Electrical Properties of Thiol-ene-based Shape Memory Polymers Intended for Flexible Electronics Frewin, Christopher L.; Ecker, Melanie; Joshi-Imre, Alexandra Polymers, Vol. 11, Issue 5 https://doi.org/10.3390/polym11050902	journal	May 2019
Degradable Poly(ether-ester-urethane)s Based on Well-Defined Aliphatic Diurethane Diisocyanate with Excellent Shape Recovery Properties at Body Temperature for Biomedical Application Xiao, Minghui; Zhang, Na; Zhuang, Jie Polymers, Vol. 11, Issue 6 https://doi.org/10.3390/polym11061002	journal	June 2019
Increased X-ray Visualization of Shape Memory Polymer Foams by Chemical Incorporation of Iodine Motifs Nash, Landon; Browning Monroe, Mary; Ding, Yong-Hong Polymers, Vol. 9, Issue 12 https://doi.org/10.3390/polym9080381	journal	August 2017
Stereolithographic 4D Bioprinting of Multiresponsive Architectures for Neural Engineering Miao, Shida; Cui, Haitao; Nowicki, Margaret Advanced Biosystems, Vol. 2, Issue 9 https://doi.org/10.1002/adbi.201800101	journal	July 2018
In Situ Generated Medical Devices Cohn, Daniel; Sloutski, Aaron; Elyashiv, Ariel Advanced Healthcare Materials, Vol. 8, Issue 8 https://doi.org/10.1002/adhm.201801066	journal	March 2019
Development of a Shape‐Memory Tube to Prevent Vascular Stenosis Shin, Yong Cheol; Lee, Jung Bok; Kim, Dae‐Hyun Advanced Materials, Vol. 31, Issue 41 https://doi.org/10.1002/adma.201904476	journal	August 2019
3D printing of shape memory poly( d , l ‐lactide‐ co ‐trimethylene carbonate) by direct ink writing for shape‐changing structures Wan, Xue; Wei, Hongqiu; Zhang, Fenghua Journal of Applied Polymer Science, Vol. 136, Issue 44 https://doi.org/10.1002/app.48177	journal	June 2019
4D Printing of Shape Memory-Based Personalized Endoluminal Medical Devices Zarek, Matt; Mansour, Nicola; Shapira, Shir Macromolecular Rapid Communications, Vol. 38, Issue 2 https://doi.org/10.1002/marc.201600628	journal	December 2016
Influence of the soft segment nature on the thermomechanical behavior of shape memory polyurethanes Sáenz-Pérez, Míriam; Laza, José Manuel; García-Barrasa, Jorge Polymer Engineering & Science, Vol. 58, Issue 2 https://doi.org/10.1002/pen.24567	journal	March 2017
Hydrogel‐coated polyurethane/urea shape memory polymer foams Dalton, Emily; Chai, Qinyuan; Shaw, Molly W. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 57, Issue 13 https://doi.org/10.1002/pola.29398	journal	May 2019
Experimental study of thermo-mechanical behavior of a thermosetting shape-memory polymer Liu, Ruoxuan; Li, Yunxin; Liu, Zishun Mechanics of Time-Dependent Materials, Vol. 23, Issue 3 https://doi.org/10.1007/s11043-018-9377-0	journal	January 2018
3D printing of thermoreversible polyurethanes with targeted shape memory and precise in situ self-healing properties Zhang, Yue; Yin, Xiang-Yu; Zheng, Mingyue Journal of Materials Chemistry A, Vol. 7, Issue 12 https://doi.org/10.1039/c8ta12428k	journal	January 2019
Surface Structures, Particles, and Fibers of Shape-Memory Polymers at Micro-/Nanoscale Cao, Liangliang; Wang, Liwei; Zhou, Cihui Advances in Polymer Technology, Vol. 2020 https://doi.org/10.1155/2020/7639724	journal	January 2020

Similar Records

Photothermal Properties of Shape Memory Polymer Micro-Actuators for Treating Stroke

Conference · Sun Mar 04 23:00:00 EST 2001 · OSTI ID:15013159

Development of Lignin-Based Polyurethane Thermoplastics

Journal Article · Mon Dec 31 23:00:00 EST 2012 · RSC Advances · OSTI ID:1097471

Laser-Activated Shape Memory Polymer Microactuator for Thrombus Removal Following Ischemic Stroke: Preliminary In Vitro Analysis

Journal Article · Thu Sep 23 00:00:00 EDT 2004 · IEEE Journal of Selected Topics in Quantum Electronics · OSTI ID:875658

Related Subjects

42 ENGINEERING
biomedical device
polyurethane
shape memory polymer
structure-property relationships
thiol-ene “click” chemistry

A Processable Shape Memory Polymer System for Biomedical Applications

Citation Formats

References (22)

Cited By (14)

Similar Records

Related Subjects