Polymeric multimaterials by photochemical patterning of crystallinity

Rylski, Adrian K.; Cater, Henry L.; Mason, Keldy S.; Allen, Marshall J.; Arrowood, Anthony J.; Freeman, Benny D.; Sanoja, Gabriel E.; Page, Zachariah A.

doi:10.1126/science.add6975

Polymeric multimaterials by photochemical patterning of crystallinity

Journal Article · 14 October 2022 · Science

DOI:https://doi.org/10.1126/science.add6975· OSTI ID:2421078

^[1]; ^[2]; ^[2]; ^[3]; ^[4]; ^[4]; ^[4]; ^[2]

Department of Chemistry, The University of Texas at Austin, Austin, TX 78712, USA.; OSTI
Department of Chemistry, The University of Texas at Austin, Austin, TX 78712, USA.
Department of Chemistry, The University of Texas at Austin, Austin, TX 78712, USA.; McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712, USA.
McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712, USA.

An organized combination of stiff and elastic domains within a single material can synergistically tailor bulk mechanical properties. However, synthetic methods to achieve such sophisticated architectures remain elusive. We report a rapid, facile, and environmentally benign method to pattern strong and stiff semicrystalline phases within soft and elastic matrices using stereo-controlled ring-opening metathesis polymerization of an industrial monomer,cis-cyclooctene. Dual polymerization catalysis dictates polyolefin backbone chemistry, which enables patterning of compositionally uniform materials with seamless stiff and elastic interfaces. Visible light–induced activation of a metathesis catalyst results in the formation of semicrystallinetranspolyoctenamer rubber, outcompeting the formation ofcispolyoctenamer rubber, which occurs at room temperature. This bottom-up approach provides a method for manufacturing polymeric materials with promising applications in soft optoelectronics and robotics.

Research Organization:: Univ. of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: SC0019272

OSTI ID:: 2421078

Journal Information:: Science, Journal Name: Science Journal Issue: 6616 Vol. 378; ISSN 0036-8075

Publisher:: AAAS

Country of Publication:: United States

Language:: English

References (36)

Solution Mask Liquid Lithography (SMaLL) for One-Step, Multimaterial 3D Printing Dolinski, Neil D.; Page, Zachariah A.; Callaway, E. Benjamin Advanced Materials, Vol. 30, Issue 31 https://doi.org/10.1002/adma.201800364	journal	June 2018
Fractal-like hierarchical organization of bone begins at the nanoscale Reznikov, Natalie; Bilton, Matthew; Lari, Leonardo Science, Vol. 360, Issue 6388 https://doi.org/10.1126/science.aao2189	journal	May 2018
Skin-Inspired Electronics: An Emerging Paradigm Wang, Sihong; Oh, Jin Young; Xu, Jie Accounts of Chemical Research, Vol. 51, Issue 5 https://doi.org/10.1021/acs.accounts.8b00015	journal	April 2018
Scrambling reaction between polymers prepared by step-growth and chain-growth polymerizations: macromolecular cross-metathesis between 1,4-polybutadiene and olefin-containing polyester Otsuka, Hideyuki; Muta, Takatoshi; Sakada, Masahide Chemical Communications, Issue 9 https://doi.org/10.1039/b818014h	journal	January 2009
Structural Orientation and Anisotropy in Biological Materials: Functional Designs and Mechanics Liu, Zengqian; Zhang, Zhefeng; Ritchie, Robert O. Advanced Functional Materials, Vol. 30, Issue 10 https://doi.org/10.1002/adfm.201908121	journal	January 2020
Two-Way Reversible Shape Memory in a Semicrystalline Network Chung, Taekwoong; Romo-Uribe, Angel; Mather, Patrick T. Macromolecules, Vol. 41, Issue 1 https://doi.org/10.1021/ma071517z	journal	January 2008
Free‐radical catalyzed oxidation reactions with cyclohexene and cyclooctene with peroxides as initiators Luck, Rudy L.; Newberry, Nick K. Journal of Physical Organic Chemistry, Vol. 35, Issue 11 https://doi.org/10.1002/poc.4326	journal	February 2022
Chemical syntheses of bioinspired and biomimetic polymers toward biobased materials Ganewatta, Mitra S.; Wang, Zhongkai; Tang, Chuanbing Nature Reviews Chemistry, Vol. 5, Issue 11 https://doi.org/10.1038/s41570-021-00325-x	journal	October 2021
The rise of plastic bioelectronics Someya, Takao; Bao, Zhenan; Malliaras, George G. Nature, Vol. 540, Issue 7633 https://doi.org/10.1038/nature21004	journal	December 2016
Ring-opening metathesis polymerization of 8-membered cyclic olefins Martinez, Henry; Ren, Ning; Matta, Megan E. Polymer Chemistry, Vol. 5, Issue 11 https://doi.org/10.1039/c3py01787g	journal	January 2014
Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis Theunissen, Cédric; Ashley, Melissa A.; Rovis, Tomislav Journal of the American Chemical Society, Vol. 141, Issue 17 https://doi.org/10.1021/jacs.8b13663	journal	April 2019
Ru-Catalyzed, cis-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability Song, Jung-Ah; Peterson, Gregory I.; Bang, Ki-Taek Journal of the American Chemical Society, Vol. 142, Issue 23 https://doi.org/10.1021/jacs.0c02785	journal	May 2020
Characterization of 3D Printed Stretching Devices for Imaging Force Transmission in Live-Cells Mayer, Carl R.; Arsenovic, Paul T.; Bathula, Kranthidhar Cellular and Molecular Bioengineering, Vol. 12, Issue 4 https://doi.org/10.1007/s12195-019-00579-y	journal	July 2019
The monoclinic structure of even trans-polyalkenamers Natta, G.; Bassi, I. W.; Fagherazzi, G. European Polymer Journal, Vol. 3, Issue 3 https://doi.org/10.1016/0014-3057(67)90003-1	journal	August 1967
Multiscale Toughening Mechanisms in Biological Materials and Bioinspired Designs Huang, Wei; Restrepo, David; Jung, Jae‐Young Advanced Materials, Vol. 31, Issue 43 https://doi.org/10.1002/adma.201901561	journal	July 2019
Crystallinity of trans-polyoctenamer: characterization and influence of sample history Schneider, W. A.; Müller, M. F. Journal of Molecular Catalysis, Vol. 46, Issue 1-3 https://doi.org/10.1016/0304-5102(88)85111-3	journal	July 1988
The Living ROMP of trans -Cyclooctene Walker, Ron; Conrad, Rosemary M.; Grubbs, Robert H. Macromolecules, Vol. 42, Issue 3 https://doi.org/10.1021/ma801693q	journal	February 2009
Tunable Mechanical Anisotropy, Crack Guiding, and Toughness Enhancement in Two‐Stage Reactive Polymer Networks Cox, Lewis M.; Blevins, Adrienne K.; Drisko, Jasper A. Advanced Engineering Materials, Vol. 21, Issue 8 https://doi.org/10.1002/adem.201900578	journal	June 2019
Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design Hotta, A.; Cochran, E.; Ruokolainen, J. Proceedings of the National Academy of Sciences, Vol. 103, Issue 42 https://doi.org/10.1073/pnas.0602894103	journal	October 2006
Stretchable heterogeneous composites with extreme mechanical gradients Libanori, Rafael; Erb, Randall M.; Reiser, Alain Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2281	journal	January 2012
Multimaterial actinic spatial control 3D and 4D printing Schwartz, J. J.; Boydston, A. J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08639-7	journal	February 2019
Synthesis of norbornene–cyclooctene copolymers by the cross-metathesis of polynorbornene with polyoctenamer Gringolts, M. L.; Denisova, Yu. I.; Shandryuk, G. A. RSC Advances, Vol. 5, Issue 1 https://doi.org/10.1039/C4RA12001A	journal	January 2015
Rupture of rubber. I. Characteristic energy for tearing Rivlin, R. S.; Thomas, A. G. Journal of Polymer Science, Vol. 10, Issue 3 https://doi.org/10.1002/pol.1953.120100303	journal	March 1953
Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life Robertson, Ian D.; Dean, Leon M.; Rudebusch, Gabriel E. ACS Macro Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsmacrolett.7b00270	journal	May 2017
Access to Disparate Soft Matter Materials by Curing with Two Colors of Light Bialas, Sabrina; Michalek, Lukas; Marschner, David E. Advanced Materials, Vol. 31, Issue 8 https://doi.org/10.1002/adma.201807288	journal	January 2019
Ruthenium–indenylidene complexes: powerful tools for metathesis transformations Boeda, Fabien; Clavier, Hervé; Nolan, Steven P. Chemical Communications, Issue 24 https://doi.org/10.1039/b718287b	journal	January 2008
Structure and mechanics of interfaces in biological materials Barthelat, Francois; Yin, Zhen; Buehler, Markus J. Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.7	journal	March 2016
Large-Strain Mechanical Behavior of Model Block Copolymer Adhesives Creton, Costantino; Hu, Guangjun; Deplace, Fanny Macromolecules, Vol. 42, Issue 20 https://doi.org/10.1021/ma900821k	journal	October 2009
Cyclic fatigue failure of TPU using a crack propagation approach Scetta, Giorgia; Selles, Nathan; Heuillet, Patrick Polymer Testing, Vol. 97 https://doi.org/10.1016/j.polymertesting.2021.107140	journal	May 2021
Chelated Ruthenium Catalysts for Z -Selective Olefin Metathesis Endo, Koji; Grubbs, Robert H. Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja202818v	journal	June 2011
Dissecting Biological and Synthetic Soft–Hard Interfaces for Tissue-Like Systems Fang, Yin; Yang, Xiao; Lin, Yiliang Chemical Reviews, Vol. 122, Issue 5 https://doi.org/10.1021/acs.chemrev.1c00365	journal	October 2021
Soft actuators for real-world applications Li, Meng; Pal, Aniket; Aghakhani, Amirreza Nature Reviews Materials, Vol. 7, Issue 3 https://doi.org/10.1038/s41578-021-00389-7	journal	November 2021
Soft Materials by Design: Unconventional Polymer Networks Give Extreme Properties Zhao, Xuanhe; Chen, Xiaoyu; Yuk, Hyunwoo Chemical Reviews, Vol. 121, Issue 8 https://doi.org/10.1021/acs.chemrev.0c01088	journal	April 2021
Stretchable materials of high toughness and low hysteresis Wang, Zhengjin; Xiang, Chunping; Yao, Xi Proceedings of the National Academy of Sciences, Vol. 116, Issue 13 https://doi.org/10.1073/pnas.1821420116	journal	March 2019
Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications Eivgi, Or; Phatake, Ravindra S.; Nechmad, Noy B. Accounts of Chemical Research, Vol. 53, Issue 10 https://doi.org/10.1021/acs.accounts.0c00495	journal	September 2020
Photoswitching Cationic and Radical Polymerizations: Spatiotemporal Control of Thermoset Properties Ma, Yuting; Kottisch, Veronika; McLoughlin, Elizabeth A. Journal of the American Chemical Society, Vol. 143, Issue 50 https://doi.org/10.1021/jacs.1c09523	journal	December 2021

Similar Records

Reactive triblock polymers from tandem ring-opening polymerization for nanostructured vinyl thermosets

Journal Article · 2013 · Polym. Chem. - UK · OSTI ID:1050081

Chemically recyclable polyolefin-like multiblock polymers

Journal Article · 2023 · Science · OSTI ID:2205316

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

Journal Article · 2025 · Journal of Polymer Science · OSTI ID:2574184

Related Subjects

Science & Technology - Other Topics

Polymeric multimaterials by photochemical patterning of crystallinity

Citation Formats

References (36)

Similar Records

Related Subjects