Spectroscopic Signatures of MQ-Resins in Silicone Elastomers

Sawvel, April M.; Crowhurst, Jonathan C.; Mason, Harris E.; Oakdale, James S.; Ruelas, Samantha; Eshelman, Hannah V.; Maxwell, Robert S.

doi:10.1021/acs.macromol.1c00086

Title: Spectroscopic Signatures of MQ-Resins in Silicone Elastomers

Journal Article · Fri Apr 23 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c00086· OSTI ID:1785911

^[1]; Crowhurst, Jonathan C. ^[1];

^[1]; Oakdale, James S. ^[1]; Ruelas, Samantha ^[1]; Eshelman, Hannah V. ^[1];

^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Polysiloxane elastomers have a large application space due to their versatile cross-linking chemistry and highly tunable physical and mechanical properties. One approach for improving the mechanical integrity of commercial polysiloxane “silicone” elastomers while maintaining their optical transparency is the addition of small, silicone-resin molecules to the network. However, both the poly(dimethylsiloxane) (PDMS) network and the silicone-resin particles have an amorphous structure and complex chemistry, which makes the characterization of their structural properties and segmental network dynamics difficult. Here, we report the synthesis and characterization of a series of model silicone networks modified with a specific class of silicone-resin known as MQ-resin using Raman and advanced nuclear magnetic resonance (NMR) spectroscopy methods. Raman spectroscopy was successfully used to quantify the contribution of the MQ-resin to the network, to determine the type of MQ-resin present in the network, and to investigate the completeness of the network cross-linking reaction. Furthermore, solid-state and 1H double-quantum (DQ) NMR spectroscopies were used not only as a detection method for the MQ-resins but also to quantify changes in the segmental dynamics of the network as a function of MQ-resin concentration. The combination of Raman and NMR spectroscopies describes a series of samples where the MQ-resin particles and PDMS chains maintain their independent segmental dynamics up to high concentrations of MQ-resins (40–50% MQ), where the physical properties of the resin dominate the physical properties of the overall network. The results from our spectroscopic analyses are consistent with the results from macroscopic characterization techniques such as solvent uptake and mechanical testing. The spectroscopic insights into the structure–property relationships of PDMS-MQ composites presented in this study are a valuable tool not only for the synthesis and reverse engineering of future generations of commercial silicone elastomers but also for understanding the mechanisms of aging and degradation over the material lifetime.

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1785911

Report Number(s):: LLNL-JRNL-817509; 1027351

Journal Information:: Macromolecules, Vol. 54, Issue 9; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

Influence of cross-linker concentration on the cross-linking of PDMS and the network structures formed Esteves, A. C. C.; Brokken-Zijp, J.; Laven, J. Polymer, Vol. 50, Issue 16 https://doi.org/10.1016/j.polymer.2009.06.022	journal	July 2009
MQ NMR and SPME Analysis of Nonlinearity in the Degradation of a Filled Silicone Elastomer Chinn, Sarah C.; Alviso, Cynthia T.; Berman, Elena S. F. The Journal of Physical Chemistry B, Vol. 114, Issue 30 https://doi.org/10.1021/jp1013797	journal	August 2010
Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization Johnson, Robert L.; Schmidt-Rohr, Klaus Journal of Magnetic Resonance, Vol. 239 https://doi.org/10.1016/j.jmr.2013.11.009	journal	February 2014
Synthesis and characterization of MQ silicone resins Sun, Fang; Hu, Yanli; Du, Hong-Guang Journal of Applied Polymer Science, Vol. 125, Issue 5 https://doi.org/10.1002/app.35194	journal	February 2012
Chemical Imaging in a Surface Forces Apparatus: Confocal Raman Spectroscopy of Confined Poly(dimethylsiloxane) Bae, Sung Chul; Lee, Hyunjung; Lin, Zhiqun Langmuir, Vol. 21, Issue 13 https://doi.org/10.1021/la050233+	journal	May 2005
Investigation of Network Heterogeneities in Filled, Trimodal, Highly Functional PDMS Networks by ¹ H Multiple Quantum NMR Gjersing, Erica; Chinn, Sarah; Giuliani, Jason R. Macromolecules, Vol. 40, Issue 14 https://doi.org/10.1021/ma0620924	journal	July 2007
Solid state NMR investigation of γ-irradiated composite siloxanes: Probing the silica/polysiloxane interface Mayer, Brian P.; Chinn, Sarah C.; Maxwell, Robert S. Polymer Degradation and Stability, Vol. 98, Issue 7 https://doi.org/10.1016/j.polymdegradstab.2013.03.021	journal	July 2013
Thermal Degradation in a Trimodal Poly(dimethylsiloxane) Network Studied by ¹ H Multiple Quantum NMR Giuliani, Jason R.; Gjersing, Erica L.; Chinn, Sarah C. The Journal of Physical Chemistry B, Vol. 111, Issue 45 https://doi.org/10.1021/jp075840f	journal	October 2007
A reliable and fast method for the solution of Fredhol integral equations of the first kind based on Tikhonov regularization Weese, Jürgen Computer Physics Communications, Vol. 69, Issue 1 https://doi.org/10.1016/0010-4655(92)90132-I	journal	February 1992
1H multiple-quantum nuclear magnetic resonance investigations of molecular order distributions in poly(dimethylsiloxane) networks: Evidence for a linear mixing law in bimodal systems Saalwächter, Kay; Ziegler, Pascal; Spyckerelle, Olivier The Journal of Chemical Physics, Vol. 119, Issue 6 https://doi.org/10.1063/1.1589000	journal	August 2003
Vibrational spectroscopic study of poly(dimethylsiloxane)-ZnO nanocomposites Bistričić, L.; Borjanović, V.; Mikac, L. Vibrational Spectroscopy, Vol. 68 https://doi.org/10.1016/j.vibspec.2013.05.005	journal	September 2013
Correction to Cross-Link Density Estimation of PDMS Networks with Precise Consideration of Networks Defects Chassé, Walter; Lang, Michael; Sommer, Jens-Uwe Macromolecules, Vol. 48, Issue 4 https://doi.org/10.1021/acs.macromol.5b00236	journal	February 2015
Characterization of PDMS model junctions and networks by solution and solid-state silicon-29 NMR spectroscopy Beshah, Kebede; Mark, James E.; Ackerman, Jerome L. Journal of Polymer Science Part B: Polymer Physics, Vol. 24, Issue 6 https://doi.org/10.1002/polb.1986.090240602	journal	June 1986
Composite-pulse and partially dipolar dephased multiCP for improved quantitative solid-state 13 C NMR Duan, Pu; Schmidt-Rohr, Klaus Journal of Magnetic Resonance, Vol. 285 https://doi.org/10.1016/j.jmr.2017.10.010	journal	December 2017
Raman, mid-infrared, near-infrared and ultraviolet–visible spectroscopy of PDMS silicone rubber for characterization of polymer optical waveguide materials Cai, Dengke; Neyer, Andreas; Kuckuk, Rüdiger Journal of Molecular Structure, Vol. 976, Issue 1-3 https://doi.org/10.1016/j.molstruc.2010.03.054	journal	July 2010
Synthesis, characterization and modification of silicone resins: An “Augmented Review” Robeyns, Constance; Picard, Loïc; Ganachaud, François Progress in Organic Coatings, Vol. 125 https://doi.org/10.1016/j.porgcoat.2018.03.025	journal	December 2018
1H multiple-quantum nuclear magnetic resonance investigations of molecular order in polymer networks. II. Intensity decay and restricted slow dynamics Saalwächter, Kay The Journal of Chemical Physics, Vol. 120, Issue 1 https://doi.org/10.1063/1.1630561	journal	January 2004
Properties of post-cured siloxane networks Quan, X. Polymer Engineering and Science, Vol. 29, Issue 20 https://doi.org/10.1002/pen.760292003	journal	October 1989
Silicone resin synthesized by tetraethoxysilane and chlorotrimethylsilane through hydrolysis-condensation reaction Kuo, Chung-Feng Jeffrey; Chen, Jiong-Bo; Shih, Chung-Yang Journal of Applied Polymer Science, Vol. 131, Issue 11 https://doi.org/10.1002/app.40317	journal	December 2013
Preparation, structure characterization, and thermal performance of phenyl-modified MQ silicone resins Xu, Xiaoqiu; Wu, Chuan; Zhang, Baohua Journal of Applied Polymer Science, Vol. 128, Issue 6 https://doi.org/10.1002/app.38638	journal	October 2012
Vibrational Spectroscopic Analysis of Silicones: A Fourier Transform-Raman and Inelastic Neutron Scattering Investigation Jayes, Linda; Hard, Andrew P.; Séné, Christophe Analytical Chemistry, Vol. 75, Issue 4 https://doi.org/10.1021/ac026012f	journal	February 2003
Quantification of radiation induced crosslinking in a commercial, toughened silicone rubber, TR55 by 1H MQ-NMR Maxwell, Robert S.; Chinn, Sarah C.; Alviso, Cynthia T. Polymer Degradation and Stability, Vol. 94, Issue 3 https://doi.org/10.1016/j.polymdegradstab.2008.10.028	journal	March 2009
Rediscovering Silicones: MQ Copolymers Flagg, Daniel H.; McCarthy, Thomas J. Macromolecules, Vol. 49, Issue 22 https://doi.org/10.1021/acs.macromol.6b01852	journal	November 2016
Solid-state high-resolution silicon-29 chemical shifts in silicates Magi, M.; Lippmaa, E.; Samoson, A. The Journal of Physical Chemistry, Vol. 88, Issue 8 https://doi.org/10.1021/j150652a015	journal	April 1984
Proton multiple-quantum NMR for the study of chain dynamics and structural constraints in polymeric soft materials Saalwachter, K. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 51, Issue 1 https://doi.org/10.1016/j.pnmrs.2007.01.001	journal	August 2007
Linking Network Microstructure to Macroscopic Properties of Siloxane Elastomers Using Combined Nuclear Magnetic Resonance and Mesoscale Computational Modeling Mayer, Brian P.; Lewicki, James P.; Weisgraber, Todd H. Macromolecules, Vol. 44, Issue 20, p. 8106-8115 https://doi.org/10.1021/ma2019039	journal	October 2011
Some Interesting Things about Polysiloxanes Mark, James E. Accounts of Chemical Research, Vol. 37, Issue 12 https://doi.org/10.1021/ar030279z	journal	December 2004
Synthesis and Properties of MQ Copolymers: Current State of Knowledge Tatarinova, Elena; Vasilenko, Nataliya; Muzafarov, Aziz Molecules, Vol. 22, Issue 10 https://doi.org/10.3390/molecules22101768	journal	October 2017
Inhomogeneities and local chain stretching in partially swollen networks Chassé, Walter; Schlögl, Sandra; Riess, Gisbert Soft Matter, Vol. 9, Issue 29 https://doi.org/10.1039/C3SM50195G	journal	January 2013
Cross-Link Density Estimation of PDMS Networks with Precise Consideration of Networks Defects Chassé, Walter; Lang, Michael; Sommer, Jens-Uwe Macromolecules, Vol. 45, Issue 2 https://doi.org/10.1021/ma202030z	journal	December 2011
Fillers for polysiloxane (“silicone”) elastomers Paul, Donald R.; Mark, James E. Progress in Polymer Science, Vol. 35, Issue 7 https://doi.org/10.1016/j.progpolymsci.2010.03.004	journal	July 2010
Investigation of molecular isomerism in polydimethylsiloxane by raman scattering Maxfield, J.; Shepherd, I. W. Chemical Physics, Vol. 2, Issue 4 https://doi.org/10.1016/0301-0104(73)80018-7	journal	December 1973
Chemical origins of permanent set in a peroxide cured filled silicone elastomer – tensile and 1H NMR analysis Chinn, Sarah; DeTeresa, Steve; Sawvel, April Polymer Degradation and Stability, Vol. 91, Issue 3 https://doi.org/10.1016/j.polymdegradstab.2005.05.035	journal	March 2006
Aging of silicone pressure-sensitive adhesives Antosik, Adrian K.; Bednarczyk, Paulina; Czech, Zbigniew Polymer Bulletin, Vol. 75, Issue 3 https://doi.org/10.1007/s00289-017-2083-2	journal	June 2017
Reduced Graphene Oxide Embedded with MQ Silicone Resin Nano-Aggregates for Silicone Rubber Composites with Enhanced Thermal Conductivity and Mechanical Performance Liang, Weijie; Ge, Xin; Ge, Jianfang Polymers, Vol. 10, Issue 11 https://doi.org/10.3390/polym10111254	journal	November 2018
Nonideality in Silicone Network Formation via Solvent Swelling and 1 H Double-Quantum NMR Sawvel, April M.; Chinn, Sarah C.; Gee, Matthew Macromolecules, Vol. 52, Issue 2 https://doi.org/10.1021/acs.macromol.8b01939	journal	December 2018
Correction: Inhomogeneities and local chain stretching in partially swollen networks Chassé, Walter; Schlögl, Sandra; Riess, Gisbert Soft Matter, Vol. 11, Issue 21 https://doi.org/10.1039/C5SM90081F	journal	January 2015
Precise dipolar coupling constant distribution analysis in proton multiple-quantum NMR of elastomers Chassé, Walter; Valentín, Juan López; Genesky, Geoffrey D. The Journal of Chemical Physics, Vol. 134, Issue 4 https://doi.org/10.1063/1.3534856	journal	January 2011

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36 MATERIALS SCIENCE
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Raman spectroscopy
nuclear magnetic resonance spectroscopy
silicones
nucleic acid structure
materials

Title: Spectroscopic Signatures of MQ-Resins in Silicone Elastomers

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