3D Printing Amorphous Polysiloxane Terpolymers via Vat Photopolymerization

Sirrine, Justin M.; Zlatanic, Alisa; Meenakshisundaram, Viswanath; Messman, Jamie M.; Williams, Christopher B.; Dvornic, Petar R.; Long, Timothy E.

doi:10.1002/macp.201800425

Title: 3D Printing Amorphous Polysiloxane Terpolymers via Vat Photopolymerization

Journal Article · Mon Jan 07 00:00:00 EST 2019 · Macromolecular Chemistry and Physics

DOI:https://doi.org/10.1002/macp.201800425· OSTI ID:1489887

^[1]; Zlatanic, Alisa ^[2]; Meenakshisundaram, Viswanath ^[3]; Messman, Jamie M. ^[4]; Williams, Christopher B. ^[3]; Dvornic, Petar R. ^[5];

^[1]

Department of Chemistry Macromolecules Innovation Institute Virginia Tech Blacksburg VA 24061 USA
Kansas Polymer Research Center Pittsburg State University Pittsburg KS 66762 USA
Department of Mechanical Engineering Macromolecules Innovation Institute Virginia Tech Blacksburg VA 24061 USA
Honeywell Federal Manufacturing &, Technologies LLC Kansas City MO 64147 USA
Department of Chemistry Pittsburg State University Pittsburg KS 66762 USA

Abstract Photocuring and vat photopolymerization (VP) additive manufacturing (AM) is reported for two families of fully amorphous poly(dimethyl siloxane) (PDMS) terpolymers containing either diphenylsiloxy (DiPhS) or diethylsiloxy (DiEtS) repeating units. A thiol‐functionalized PDMS crosslinker enables rapid crosslinking in air using efficient thiol–ene addition. Differential scanning calorimetry and dynamic mechanical analysis (DMA) confirm the absence of crystallinity for the DiPhS‐containing systems, while DMA shows a rubbery plateau extending to greater than 200 °C for the DiEtS‐containing system. VP‐AM of both photopolymer systems afford well‐defined 3D geometries, including high aspect ratio structures, which demonstrate feasibility of these photopolymers for the 3D printing of unique geometric objects that require elastomeric performance to temperatures as low as −120 °C.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 1489887

Journal Information:: Macromolecular Chemistry and Physics, Journal Name: Macromolecular Chemistry and Physics Vol. 220 Journal Issue: 4; ISSN 1022-1352

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

Citation Metrics:

Cited by: 29 works

Citation information provided by
Web of Science

References (42)

Silicone Elastomer Developments 1967–1977 Warrick, E. L.; Pierce, O. R.; Polmanteer, K. E. Rubber Chemistry and Technology, Vol. 52, Issue 3 https://doi.org/10.5254/1.3535229	journal	July 1979
Conformations of poly(diethylsiloxane) and its mesophase transitions Miller, Kenneth J.; Grebowicz, Janusz; Wesson, John P. Macromolecules, Vol. 23, Issue 3 https://doi.org/10.1021/ma00205a026	journal	May 1990
Can the gel point of a cross-linking polymer be detected by theG? -G? crossover? Winter, H. H. Polymer Engineering and Science, Vol. 27, Issue 22 https://doi.org/10.1002/pen.760272209	journal	December 1987
Influence of soft segment molecular weight on the mechanical hysteresis and set behavior of silicone-urea copolymers with low hard segment contents Yilgor, Iskender; Eynur, Tugba; Bilgin, Sevilay Polymer, Vol. 52, Issue 2 https://doi.org/10.1016/j.polymer.2010.11.040	journal	January 2011
Advantages and drawbacks of Thiol-ene based resins for 3D-printing Leonards, Holger; Engelhardt, Sascha; Hoffmann, Andreas SPIE LASE, SPIE Proceedings https://doi.org/10.1117/12.2081169	conference	March 2015
Ultrafast diffusion-controlled thiol–ene based crosslinking of silicone elastomers with tailored mechanical properties for biomedical applications Nguyen, Khai D. Q.; Megone, William V.; Kong, Dexu Polymer Chemistry, Vol. 7, Issue 33 https://doi.org/10.1039/C6PY01134A	journal	January 2016
Design and synthesis of non-crystallizable, low-T _g polysiloxane elastomers with functional epoxy groups through anionic copolymerization and subsequent epoxidation Meng, Yang; Chu, Junfeng; Xue, Jiajia RSC Adv., Vol. 4, Issue 59 https://doi.org/10.1039/C4RA02293A	journal	January 2014
A Review on Silicone Rubber Shit, Subhas C.; Shah, Pathik National Academy Science Letters, Vol. 36, Issue 4 https://doi.org/10.1007/s40009-013-0150-2	journal	July 2013
Advances in room temperature curing adhesives and sealants—a review Melody, David P. British Polymer Journal, Vol. 21, Issue 2 https://doi.org/10.1002/pi.4980210213	journal	January 1989
Supercooling of polydimethylsiloxane Helmer, J. D.; Polmanteer, K. E. Journal of Applied Polymer Science, Vol. 13, Issue 10 https://doi.org/10.1002/app.1969.070131008	journal	October 1969
Poly(dimethylsiloxane-co-diphenylsiloxanes): synthesis, characterization, and sequence analysis Babu, G. N.; Christopher, S. S.; Newmark, R. A. Macromolecules, Vol. 20, Issue 11 https://doi.org/10.1021/ma00177a003	journal	November 1987
Photo-curable siloxane hybrid material fabricated by a thiol–ene reaction of sol–gel synthesized oligosiloxanes Kim, Joon-Soo; Yang, SeungCheol; Park, HyungJin Chemical Communications, Vol. 47, Issue 21 https://doi.org/10.1039/c1cc11297j	journal	January 2011
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
Hydrogen bonding: a critical parameter in designing silicone copolymers Yılgör, E. Polymer, Vol. 42, Issue 19 https://doi.org/10.1016/S0032-3861(01)00293-2	journal	September 2001
Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized ¹³ C MR with Photosensitive Metabolic Substrates Marco-Rius, Irene; Cheng, Tian; Gaunt, Adam P. Journal of the American Chemical Society, Vol. 140, Issue 43 https://doi.org/10.1021/jacs.8b09326	journal	October 2018
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
Applications of Photocurable PMMS Thiol−Ene Stamps in Soft Lithography Campos, Luis M.; Truong, Tu T.; Shim, Dong Eun Chemistry of Materials, Vol. 21, Issue 21 https://doi.org/10.1021/cm902506a	journal	November 2009
Highly Versatile and Robust Materials for Soft Imprint Lithography Based on Thiol-ene Click Chemistry Campos, Luis M.; Meinel, Ines; Guino, Rosette G. Advanced Materials, Vol. 20, Issue 19 https://doi.org/10.1002/adma.200800330	journal	October 2008
Additive manufacturing of polymer-derived ceramics Eckel, Z. C.; Zhou, C.; Martin, J. H. Science, Vol. 351, Issue 6268 https://doi.org/10.1126/science.aad2688	journal	December 2015
A microstereolithography resin based on thiol-ene chemistry: towards biocompatible 3D extracellular constructs for tissue engineering Barker, Ian A.; Ablett, Matthew P.; Gilbert, Hamish T. J. Biomater. Sci., Vol. 2, Issue 4 https://doi.org/10.1039/C3BM60290G	journal	January 2014
Polydimethylsiloxane thermal degradation Part 1. Kinetic aspects Camino, G.; Lomakin, S. M.; Lazzari, M. Polymer, Vol. 42, Issue 6 https://doi.org/10.1016/S0032-3861(00)00652-2	journal	March 2001
Structure and Phase Transitions of Poly(diethylsiloxane) Molenberg, Aart; Möller, Martin Macromolecules, Vol. 30, Issue 26 https://doi.org/10.1021/ma970786u	journal	December 1997
Low Modulus Dry Silicone-Gel Materials by Photoinduced Thiol–Ene Chemistry van den Berg, Otto; Nguyen, Le-Thu T.; Teixeira, Roberto F. A. Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma402564a	journal	February 2014
Suppression of Crystallization in Polydimethylsiloxanes and Chain Branching in Their Phenyl-Containing Copolymers Zlatanic, Alisa; Radojcic, Dragana; Wan, Xianmei Macromolecules, Vol. 50, Issue 9 https://doi.org/10.1021/acs.macromol.7b00474	journal	April 2017
Studies of cyclic and linear poly(dimethylsiloxanes): 19. Glass transition temperatures and crystallization behaviour Clarson, S. J.; Dodgson, K.; Semlyen, J. A. Polymer, Vol. 26, Issue 6 https://doi.org/10.1016/0032-3861(85)90140-5	journal	June 1985
A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism Zheng, Peiwen; McCarthy, Thomas J. Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja2113257	journal	January 2012
3D Printing All-Aromatic Polyimides using Mask-Projection Stereolithography: Processing the Nonprocessable Hegde, Maruti; Meenakshisundaram, Viswanath; Chartrain, Nicholas Advanced Materials, Vol. 29, Issue 31 https://doi.org/10.1002/adma.201701240	journal	June 2017
Monitoring of the Course of the Silanolate-Initiated Polymerization of Cyclic Siloxanes. A Mechanism for the Copolymerization of Dimethyl and Diphenyl Monomers Zlatanic, Alisa; Radojcic, Dragana; Wan, Xianmei Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1021/acs.macromol.7b02658	journal	February 2018
Kinetics of thiol-ene and thiol-acrylate photopolymerizations with real-time fourier transform infrared Cramer, Neil B.; Bowman, Christopher N. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 39, Issue 19 https://doi.org/10.1002/pola.1314	journal	January 2001
Silicone containing copolymers: Synthesis, properties and applications Yilgör, Emel; Yilgör, Iskender Progress in Polymer Science, Vol. 39, Issue 6 https://doi.org/10.1016/j.progpolymsci.2013.11.003	journal	June 2014
Functional siloxanes with photo-activated, simultaneous chain extension and crosslinking for lithography-based 3D printing Sirrine, Justin M.; Meenakshisundaram, Viswanath; Moon, Nicholas G. Polymer, Vol. 152 https://doi.org/10.1016/j.polymer.2018.02.056	journal	September 2018
Beyond PDMS: off-stoichiometry thiol–ene (OSTE) based soft lithography for rapid prototyping of microfluidic devices Carlborg, Carl Fredrik; Haraldsson, Tommy; Öberg, Kim Lab on a Chip, Vol. 11, Issue 18 https://doi.org/10.1039/c1lc20388f	journal	January 2011
Synthesis and characterization of poly(diethylsiloxane) and its copolymers with different diorganosiloxane units Liu, Lihua; Yang, Shiyan; Zhang, Zhijie Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 17 https://doi.org/10.1002/pola.10822	journal	July 2003
Click chemistry stereolithography for soft robots that self-heal Wallin, T. J.; Pikul, J. H.; Bodkhe, S. Journal of Materials Chemistry B, Vol. 5, Issue 31 https://doi.org/10.1039/C7TB01605K	journal	January 2017
Well defined columnar liquid crystalline polydiethylsiloxane Molenberg, Aart; Siffrin, Stefan; Möller, Martin Macromolecular Symposia, Vol. 102, Issue 1 https://doi.org/10.1002/masy.19961020125	journal	January 1996
Some physical properties of polyorganosiloxanes. I. Linear polyorganosiloxanes Andrianov, K. A.; Slonimski??, G. L.; Zhdanov, A. A. Journal of Polymer Science Part A-1: Polymer Chemistry, Vol. 10, Issue 1 https://doi.org/10.1002/pol.1972.150100101	journal	January 1972
The effect of cure rate on the mechanical properties of dental resins Lovell, Lale G.; Lu, Hui; Elliott, Jeannine E. Dental Materials, Vol. 17, Issue 6 https://doi.org/10.1016/S0109-5641(01)00010-0	journal	November 2001
Silicone sealants and structural adhesives de Buyl, François International Journal of Adhesion and Adhesives, Vol. 21, Issue 5 https://doi.org/10.1016/S0143-7496(01)00018-5	journal	January 2001
Photocrosslinking of Silicones. Part 13. Photoinduced Thiol-Ene Crosslinking of Modified Silicones Müller, Uwe; Kunze, Annett; Herzig, Christian Journal of Macromolecular Science, Part A, Vol. 33, Issue 4 https://doi.org/10.1080/10601329608010869	journal	April 1996
The Nature of the Silicon–Oxygen Bond Weinhold, Frank; West, Robert Organometallics, Vol. 30, Issue 21 https://doi.org/10.1021/om200675d	journal	November 2011
Detailed Kinetic and Mechanistic Insight into Radical Polymerization by Spectroscopic Techniques Buback, Michael; Schroeder, Hendrik; Kattner, Hendrik Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.5b02660	journal	March 2016
Principles of Polymerization Odian, George https://doi.org/10.1002/047147875X	book	January 2004

Similar Records

Rheology guiding the design and printability of aqueous colloidal composites for additive manufacturing

Journal Article · Mon Apr 24 00:00:00 EDT 2023 · Journal of Vinyl & Additive Technology · OSTI ID:1489887

Bean, Ren H.; Rau, Daniel A.; Williams, Christopher B.; +1 more

Additive manufacturing: Frameworks for chemical understanding and advancement in vat photopolymerization

Journal Article · Mon Jul 11 00:00:00 EDT 2022 · MRS Bulletin · OSTI ID:1489887

Schwartz, Johanna J.

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination

Journal Article · Mon Jul 03 00:00:00 EDT 2023 · Additive Manufacturing · OSTI ID:1489887

Chandler, Caleb; Porcincula, Dominique H.; Ford, Michael J.; +5 more

Title: 3D Printing Amorphous Polysiloxane Terpolymers via Vat Photopolymerization

Citation Formats

References (42)

Similar Records

Related Subjects