Liquid crystalline networks based on photo-initiated thiol–ene click chemistry

Li, Yuzhan; Zhang, Yuehong; Goswami, Monojoy; Vincent, Dan; Wang, Liwei; Liu, Tuan; Li, Kai; Keum, Jong K.; Gao, Zhenhua; Ozcan, Soydan; Gluesenkamp, Kyle R.; Rios, Orlando; Kessler, Michael R.

doi:10.1039/C9SM01818B

Title: Liquid crystalline networks based on photo-initiated thiol–ene click chemistry

Journal Article · 10 December 2019 · Soft Matter (Online)

DOI: https://doi.org/10.1039/C9SM01818B · OSTI ID:1649610

^[1]; Zhang, Yuehong ^[2];

^[1]; Vincent, Dan ^[3]; Wang, Liwei ^[3]; Liu, Tuan ^[3]; Li, Kai ^[1];

^[1]; Gao, Zhenhua ^[2];

^[1];

^[1]; Kessler, Michael R. ^[4]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Shannxi Univ. of Science and Technology, Xi'an (China)
Washington State Univ., Pullman, WA (United States)
North Dakota State Univ., Fargo, ND (United States)

Photo-initiated thiol–ene click chemistry is used to develop shape memory liquid crystalline networks (LCNs). A biphenyl-based di-vinyl monomer is synthesized and cured with a di-thiol chain extender and a tetra-thiol crosslinker using UV light. The effects of photo-initiator concentration and UV light intensity on the curing behavior and liquid crystalline (LC) properties of the LCNs are investigated. The chemical composition is found to significantly influence the microstructure and the related thermomechanical properties of the LCNs. The structure–property relationship is further explored using molecular dynamics simulations, revealing that the introduction of the chain extender promotes the formation of an ordered smectic LC phase instead of agglomerated structures. The concentration of the chain extender affects the liquid crystallinity of the LCNs, resulting in distinct thermomechanical and shape memory properties. Finally, this class of LCNs exhibits fast curing rates, high conversion levels, and tailorable liquid crystallinity, making it a promising material system for advanced manufacturing, where complex and highly ordered structures can be produced with fast reaction kinetics and low energy consumption.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1649610

Alternate ID(s):: OSTI ID: 1580135

Journal Information:: Soft Matter (Online), Vol. 16, Issue 7; ISSN 1744-6848

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 12 works

Citation information provided by
Web of Science

References (62)

Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds Pei, Zhiqiang; Yang, Yang; Chen, Qiaomei Nature Materials, Vol. 13, Issue 1 https://doi.org/10.1038/nmat3812	journal	December 2013
Photoresponsive Liquid Crystalline Epoxy Networks with Shape Memory Behavior and Dynamic Ester Bonds Li, Yuzhan; Rios, Orlando; Keum, Jong K. ACS Applied Materials & Interfaces, Vol. 8, Issue 24 https://doi.org/10.1021/acsami.6b04374	journal	June 2016
Liquid crystalline epoxy networks with exchangeable disulfide bonds Li, Yuzhan; Zhang, Yuehong; Rios, Orlando Soft Matter, Vol. 13, Issue 29 https://doi.org/10.1039/C7SM00934H	journal	January 2017
3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order Kotikian, Arda; Truby, Ryan L.; Boley, John William Advanced Materials, Vol. 30, Issue 10 https://doi.org/10.1002/adma.201706164	journal	January 2018
Tough, Shape-Changing Materials: Crystallized Liquid Crystal Elastomers Kim, Hyun; Boothby, Jennifer M.; Ramachandran, Sarvesh Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00567	journal	May 2017
Viscoelasticity of the polydomain-monodomain transition in main-chain liquid crystal elastomers Azoug, A.; Vasconcellos, V.; Dooling, J. Polymer, Vol. 98 https://doi.org/10.1016/j.polymer.2016.06.022	journal	August 2016
Printed artificial cilia from liquid-crystal network actuators modularly driven by light van Oosten, Casper L.; Bastiaansen, Cees W. M.; Broer, Dirk J. Nature Materials, Vol. 8, Issue 8 https://doi.org/10.1038/nmat2487	journal	June 2009
Soft shape memory in main-chain liquid crystalline elastomers Burke, Kelly A.; Mather, Patrick T. Journal of Materials Chemistry, Vol. 20, Issue 17 https://doi.org/10.1039/b924050k	journal	January 2010
High strain actuation liquid crystal elastomers via modulation of mesophase structure Saed, Mohand O.; Volpe, Ross H.; Traugutt, Nicholas A. Soft Matter, Vol. 13, Issue 41 https://doi.org/10.1039/C7SM01380A	journal	January 2017
Fast liquid-crystal elastomer swims into the dark Camacho-Lopez, Miguel; Finkelmann, Heino; Palffy-Muhoray, Peter Nature Materials, Vol. 3, Issue 5 https://doi.org/10.1038/nmat1118	journal	April 2004
Nematic main-chain elastomers: Coupling and orientational behavior Krause, Simon; Zander, Frank; Bergmann, Gerd Comptes Rendus Chimie, Vol. 12, Issue 1-2 https://doi.org/10.1016/j.crci.2008.08.003	journal	January 2009
Accordion-like Actuators of Multiple 3D Patterned Liquid Crystal Polymer Films de Haan, Laurens T.; Gimenez-Pinto, Vianney; Konya, Andrew Advanced Functional Materials, Vol. 24, Issue 9 https://doi.org/10.1002/adfm.201302568	journal	October 2013
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
Liquid crystalline epoxy resin based on biphenyl mesogen: Thermal characterization Li, Yuzhan; Badrinarayanan, Prashanth; Kessler, Michael R. Polymer, Vol. 54, Issue 12 https://doi.org/10.1016/j.polymer.2013.03.043	journal	May 2013
Effects of Monomer Structure on Their Organization and Polymerization in a Smectic Liquid Crystal Guymon, C. A. Science, Vol. 275, Issue 5296 https://doi.org/10.1126/science.275.5296.57	journal	January 1997
Voxelated liquid crystal elastomers Ware, Taylor H.; McConney, Michael E.; Wie, Jeong Jae Science, Vol. 347, Issue 6225 https://doi.org/10.1126/science.1261019	journal	February 2015
Polymers for 3D Printing and Customized Additive Manufacturing Ligon, Samuel Clark; Liska, Robert; Stampfl, Jürgen Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00074	journal	July 2017
Thiol-ene “click” reactions and recent applications in polymer and materials synthesis Lowe, Andrew B. Polym. Chem., Vol. 1, Issue 1 https://doi.org/10.1039/B9PY00216B	journal	January 2010
Programmed morphing of liquid crystal networks de Haan, Laurens T.; Schenning, Albertus P. H. J.; Broer, Dirk J. Polymer, Vol. 55, Issue 23 https://doi.org/10.1016/j.polymer.2014.08.023	journal	November 2014
Liquid-crystal order during synthesis affects main-chain liquid-crystal elastomer behavior Traugutt, N. A.; Volpe, R. H.; Bollinger, M. S. Soft Matter, Vol. 13, Issue 39 https://doi.org/10.1039/C7SM01405H	journal	January 2017
Molecular engineering of step-growth liquid crystal elastomers Zhu, B.; Barnes, M. G.; Kim, H. Sensors and Actuators B: Chemical, Vol. 244 https://doi.org/10.1016/j.snb.2016.12.141	journal	June 2017
Cure kinetics of liquid crystalline epoxy resins based on biphenyl mesogen Li, Yuzhan; Kessler, Michael R. Journal of Thermal Analysis and Calorimetry, Vol. 117, Issue 1 https://doi.org/10.1007/s10973-014-3647-0	journal	March 2014
A hydrogel-forming liquid crystalline elastomer exhibiting soft shape memory Torbati, Amir H.; Mather, Patrick T. Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 1 https://doi.org/10.1002/polb.23892	journal	September 2015
Elastocaloric effect in liquid crystal elastomers from molecular simulations Skačej, Gregor Liquid Crystals, Vol. 45, Issue 13-15 https://doi.org/10.1080/02678292.2018.1492035	journal	June 2018
A Simple and Versatile Synthetic Route for the Preparation of Main-Chain, Liquid-Crystalline Elastomers Donnio, Bertrand; Wermter, Hendrik; Finkelmann, Heino Macromolecules, Vol. 33, Issue 21 https://doi.org/10.1021/ma0002850	journal	October 2000
Soft Elasticity in Main Chain Liquid Crystal Elastomers Dey, Sonal; Agra-Kooijman, Dena; Ren, Wanting Crystals, Vol. 3, Issue 2 https://doi.org/10.3390/cryst3020363	journal	June 2013
Thiol–Ene Elastomers Derived from Biobased Phenolic Acids with Varying Functionality Yang, Guozhen; Kristufek, Samantha L.; Link, Lauren A. Macromolecules, Vol. 49, Issue 20 https://doi.org/10.1021/acs.macromol.6b01018	journal	October 2016
Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding Zhao, Qian; Qi, H. Jerry; Xie, Tao Progress in Polymer Science, Vol. 49-50 https://doi.org/10.1016/j.progpolymsci.2015.04.001	journal	October 2015
Shape memory polymers: Past, present and future developments Hager, Martin D.; Bode, Stefan; Weber, Christine Progress in Polymer Science, Vol. 49-50 https://doi.org/10.1016/j.progpolymsci.2015.04.002	journal	October 2015
Dynamic self-stiffening in liquid crystal elastomers Agrawal, Aditya; Chipara, Alin C.; Shamoo, Yousif Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2772	journal	April 2013
Photoinduced Topographical Feature Development in Blueprinted Azobenzene-Functionalized Liquid Crystalline Elastomers Ahn, Suk-kyun; Ware, Taylor H.; Lee, Kyung Min Advanced Functional Materials, Vol. 26, Issue 32 https://doi.org/10.1002/adfm.201601090	journal	July 2016
The mechanical and magnetic alignment of liquid crystalline epoxy thermosets Barclay, G. G.; McNamee, S. G.; Ober, C. K. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 30, Issue 9 https://doi.org/10.1002/pola.1992.080300907	journal	August 1992
Four-dimensional Printing of Liquid Crystal Elastomers Ambulo, Cedric P.; Burroughs, Julia J.; Boothby, Jennifer M. ACS Applied Materials & Interfaces, Vol. 9, Issue 42 https://doi.org/10.1021/acsami.7b11851	journal	October 2017
Multifunctional Shape-Memory Polymers Behl, Marc; Razzaq, Muhammad Yasar; Lendlein, Andreas Advanced Materials, Vol. 22, Issue 31 https://doi.org/10.1002/adma.200904447	journal	June 2010
Photopolymerizations of Thiol−Ene Polymers without Photoinitiators Cramer, Neil B.; Scott, J. Paul; Bowman, Christopher N. Macromolecules, Vol. 35, Issue 14 https://doi.org/10.1021/ma0200672	journal	July 2002
Engineering of Complex Order and the Macroscopic Deformation of Liquid Crystal Polymer Networks de Haan, Laurens T.; Sánchez-Somolinos, Carlos; Bastiaansen, Cees M. W. Angewandte Chemie International Edition, Vol. 51, Issue 50 https://doi.org/10.1002/anie.201205964	journal	November 2012
Thermomechanical properties of monodomain nematic main-chain liquid crystal elastomers Merkel, Daniel R.; Traugutt, Nicholas A.; Visvanathan, Rayshan Soft Matter, Vol. 14, Issue 29 https://doi.org/10.1039/C8SM01178H	journal	January 2018
Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer Li, Yuzhan; Pruitt, Cole; Rios, Orlando Macromolecules, Vol. 48, Issue 9 https://doi.org/10.1021/acs.macromol.5b00519	journal	April 2015
Thiol-acrylate main-chain liquid-crystalline elastomers with tunable thermomechanical properties and actuation strain Saed, Mohand O.; Torbati, Amir H.; Starr, Chelsea A. Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 2 https://doi.org/10.1002/polb.24249	journal	October 2016
Uniaxial and Shear Deformations in Smectic-C Main-Chain Liquid-Crystalline Elastomers Sánchez-Ferrer, Antoni; Finkelmann, Heino Macromolecules, Vol. 41, Issue 3 https://doi.org/10.1021/ma7025644	journal	February 2008
Conversion of light into macroscopic helical motion Iamsaard, Supitchaya; Aßhoff, Sarah J.; Matt, Benjamin Nature Chemistry, Vol. 6, Issue 3 https://doi.org/10.1038/nchem.1859	journal	February 2014
Recent advances in shape–memory polymers: Structure, mechanism, functionality, modeling and applications Hu, Jinlian; Zhu, Yong; Huang, Huahua Progress in Polymer Science, Vol. 37, Issue 12 https://doi.org/10.1016/j.progpolymsci.2012.06.001	journal	December 2012
Liquid crystal elastomer actuators: Synthesis, alignment, and applications Kularatne, Ruvini S.; Kim, Hyun; Boothby, Jennifer M. Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 5 https://doi.org/10.1002/polb.24287	journal	January 2017
Preparation and characterization of side-chain liquid crystal polymer/paraffin composites as form-stable phase change materials Wu, Dang; Ni, Bin; Liu, Yujie Journal of Materials Chemistry A, Vol. 3, Issue 18 https://doi.org/10.1039/C5TA00606F	journal	January 2015
Liquid Crystalline Elastomers as Actuators and Sensors Ohm, Christian; Brehmer, Martin; Zentel, Rudolf Advanced Materials, Vol. 22, Issue 31 https://doi.org/10.1002/adma.200904059	journal	May 2010
Thiol-enes: Chemistry of the past with promise for the future Hoyle, Charles E.; Lee, Tai Yeon; Roper, Todd Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 21 https://doi.org/10.1002/pola.20366	journal	January 2004
4D Printed Actuators with Soft-Robotic Functions López-Valdeolivas, María; Liu, Danqing; Broer, Dick Jan Macromolecular Rapid Communications, Vol. 39, Issue 5 https://doi.org/10.1002/marc.201700710	journal	December 2017
Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers White, Timothy J.; Broer, Dirk J. Nature Materials, Vol. 14, Issue 11 https://doi.org/10.1038/nmat4433	journal	October 2015
Topography from Topology: Photoinduced Surface Features Generated in Liquid Crystal Polymer Networks McConney, Michael E.; Martinez, Angel; Tondiglia, Vincent P. Advanced Materials, Vol. 25, Issue 41 https://doi.org/10.1002/adma.201301891	journal	July 2013
Electrocaloric and elastocaloric effects in soft materials Trček, Maja; Lavrič, Marta; Cordoyiannis, George Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2074 https://doi.org/10.1098/rsta.2015.0301	journal	August 2016
Liquid-Crystalline Elastomer Microvalve for Microfluidics Sánchez-Ferrer, Antoni; Fischl, Tamás; Stubenrauch, Mike Advanced Materials, Vol. 23, Issue 39 https://doi.org/10.1002/adma.201102277	journal	September 2011
Photo-responsive liquid crystalline epoxy networks with exchangeable disulfide bonds Li, Yuzhan; Zhang, Yuehong; Rios, Orlando RSC Advances, Vol. 7, Issue 59 https://doi.org/10.1039/C7RA06343A	journal	January 2017
What creates liquid crystal phases? Luckhurst, Geoffrey R. Liquid Crystals Today, Vol. 3, Issue 1 https://doi.org/10.1080/13583149308628610	journal	March 1993
New directions in the chemistry of shape memory polymers Berg, Gayla J.; McBride, Matthew K.; Wang, Chen Polymer, Vol. 55, Issue 23 https://doi.org/10.1016/j.polymer.2014.07.052	journal	November 2014
Shape-memory polymers and their composites: Stimulus methods and applications Leng, Jinsong; Lan, Xin; Liu, Yanju Progress in Materials Science, Vol. 56, Issue 7 https://doi.org/10.1016/j.pmatsci.2011.03.001	journal	September 2011
Making waves in a photoactive polymer film Gelebart, Anne Helene; Jan Mulder, Dirk; Varga, Michael Nature, Vol. 546, Issue 7660 https://doi.org/10.1038/nature22987	journal	June 2017
Combined One-Way and Two-Way Shape Memory in a Glass-Forming Nematic Network Qin, Haihu; Mather, Patrick T. Macromolecules, Vol. 42, Issue 1 https://doi.org/10.1021/ma8022926	journal	January 2009
Adaptable liquid crystal elastomers with transesterification-based bond exchange reactions Hanzon, Drew W.; Traugutt, Nicholas A.; McBride, Matthew K. Soft Matter, Vol. 14, Issue 6 https://doi.org/10.1039/C7SM02110K	journal	January 2018
Thiol–ene “click” reactions and recent applications in polymer and materials synthesis: a first update Lowe, Andrew B. Polym. Chem., Vol. 5, Issue 17 https://doi.org/10.1039/C4PY00339J	journal	January 2014
Tailorable and programmable liquid-crystalline elastomers using a two-stage thiol–acrylate reaction Yakacki, C. M.; Saed, M.; Nair, D. P. RSC Advances, Vol. 5, Issue 25 https://doi.org/10.1039/C5RA01039J	journal	January 2015
Programmable Liquid Crystal Elastomers Prepared by Thiol–Ene Photopolymerization Ware, Taylor H.; Perry, Zachary P.; Middleton, Claire M. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00511	journal	August 2015
Engineering of Complex Order and the Macroscopic Deformation of Liquid Crystal Polymer Networks de Haan, Laurens T.; Sánchez-Somolinos, Carlos; Bastiaansen, Cees M. W. Angewandte Chemie, Vol. 124, Issue 50 https://doi.org/10.1002/ange.201205964	journal	November 2012

Similar Records

Fluoroalkyl-functional imidazoles and imidazolium–based ionic liquids prepared via thiol-ene/yne click chemistry

Journal Article · 2019 · Journal of Molecular Liquids · OSTI ID:1580419

Moore, Levi M. J.; Greeson, Kevin T.; Redeker, Neil D.; +9 more

Composition for thiol-ene-based polymerization and liquid crystalline network-containing objects formed therefrom using additive manufacturing

Patent · 2023 · OSTI ID:2222009

Rios, Orlando; Carter, William G.; Kessler, Michael R.; +2 more

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

Journal Article · 2015 · Macromolecules · OSTI ID:1324048

Li, Yuzhan; Pruitt, Cole; Rios, Orlando; +5 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Liquid crystalline networks based on photo-initiated thiol–ene click chemistry

Citation Formats

References (62)

Similar Records

Related Subjects