Nonideality in Silicone Network Formation via Solvent Swelling and 1H Double-Quantum NMR

Sawvel, April M.; Chinn, Sarah C.; Gee, Matthew; Loeb, Colin K.; Maiti, Amitesh; Mason, Harris E.; Maxwell, Robert S.; Lewicki, James P.

doi:10.1021/acs.macromol.8b01939

Title: Nonideality in Silicone Network Formation via Solvent Swelling and ¹H Double-Quantum NMR

Journal Article · Fri Dec 28 00:00:00 EST 2018 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.8b01939· OSTI ID:1512609

^[1]; Chinn, Sarah C. ^[1]; Gee, Matthew ^[1]; Loeb, Colin K. ^[1]; Maiti, Amitesh ^[1];

^[2]; Maxwell, Robert S. ^[1];

^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate, Materials Science Division
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate, Atmospheric, Earth, and Energy Division

The versatile crosslinking chemistry of poly(dimethylsiloxane) (PDMS) based materials affords a large research space in which polymers with widely varying elastomeric properties may be synthesized. Parameters such as chain length, crosslink density, crosslink functionality, filler content, and chain chemistry can all be modified to produce materials with specific physical and mechanical properties. Commercial polysiloxane based, ‘silicone’ elastomers are generally intractable, which makes the precise characterization of their networks problematic. We report here the application of equilibrium solvent uptake analysis and ¹H double-quantum nuclear magnetic resonance (¹H DQ NMR) spectroscopy to determine the network topology of end-linked PDMS networks with non-ideal network topology. Despite their structural complexity, we can quantify both the classical and non-classical contributions to network structure using ¹H DQ NMR which are in reasonable agreement with solvent uptake data. These findings serve as the foundation for future investigations of even more complex commercial silicones using ¹H DQ NMR.

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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:: 1512609

Report Number(s):: LLNL-JRNL-757701; 945630

Journal Information:: Macromolecules, Vol. 52, Issue 2; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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References (35)

Model networks of end‐linked polydimethylsiloxane chains. I. Comparisons between experimental and theoretical values of the elastic modulus and the equilibrium degree of swelling Mark, J. E.; Sullivan, J. L. The Journal of Chemical Physics, Vol. 66, Issue 3 https://doi.org/10.1063/1.434056	journal	February 1977
Entanglement Effects in Elastomers: Macroscopic vs Microscopic Properties Schlögl, Sandra; Trutschel, Marie-Luise; Chassé, Walter Macromolecules, Vol. 47, Issue 9 https://doi.org/10.1021/ma4026064	journal	April 2014
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
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
Structure and swelling of polymer networks: insights from NMR Saalwächter, Kay; Chassé, Walter; Sommer, Jens-Uwe Soft Matter, Vol. 9, Issue 29 https://doi.org/10.1039/c3sm50194a	journal	January 2013
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
Radiation-Induced Cross-Linking in a Silica-Filled Silicone Elastomer As Investigated by Multiple Quantum ¹ H NMR Maxwell, Robert S.; Chinn, Sarah C.; Solyom, David Macromolecules, Vol. 38, Issue 16 https://doi.org/10.1021/ma047625s	journal	August 2005
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
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
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
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
The effects of γ-radiation on the thermal, mechanical, and segmental dynamics of a silica filled, room temperature vulcanized polysiloxane rubber Maxwell, Robert S.; Cohenour, Rebecca; Sung, William Polymer Degradation and Stability, Vol. 80, Issue 3 https://doi.org/10.1016/S0141-3910(03)00028-4	journal	January 2003
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
Compression set in gas-blown condensation-cured polysiloxane elastomers Patel, Mogon; Chinn, Sarah; Maxwell, Robert S. Polymer Degradation and Stability, Vol. 95, Issue 12 https://doi.org/10.1016/j.polymdegradstab.2010.07.038	journal	December 2010
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
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
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
Detection of Heterogeneities in Dry and Swollen Polymer Networks by Proton Low-Field NMR Spectroscopy Saalwächter, Kay Journal of the American Chemical Society, Vol. 125, Issue 48 https://doi.org/10.1021/ja038278p	journal	December 2003
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
Statistical Mechanics of Cross‐Linked Polymer Networks II. Swelling Flory, Paul J.; Rehner, John The Journal of Chemical Physics, Vol. 11, Issue 11 https://doi.org/10.1063/1.1723792	journal	November 1943
Thermodynamic interaction parameters in polymer solutions and gels Horkay, Ferenc; Hecht, Anne-Marie; Geissler, Erik Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 11 https://doi.org/10.1002/polb.1995.090331109	journal	August 1995
Suppression of signals from the probe in bloch decay spectra Cory, D. G.; Ritchey, W. M. Journal of Magnetic Resonance (1969), Vol. 80, Issue 1 https://doi.org/10.1016/0022-2364(88)90064-9	journal	October 1988
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
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
Real-Time Observation of Polymer Network Formation by Liquid- and Solid-State NMR Revealing Multistage Reaction Kinetics Kovermann, Michael; Saalwächter, Kay; Chassé, Walter The Journal of Physical Chemistry B, Vol. 116, Issue 25 https://doi.org/10.1021/jp302745a	journal	June 2012
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
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
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
Mechanical and swelling properties of PDMS interpenetrating polymer networks Yoo, Seong Hyun; Cohen, Claude; Hui, Chung-Yuen Polymer, Vol. 47, Issue 17 https://doi.org/10.1016/j.polymer.2006.06.035	journal	August 2006
Effect of network structure on the stress–strain behaviour of endlinked PDMS elastomers Yoo, Seong Hyun; Yee, Leslie; Cohen, Claude Polymer, Vol. 51, Issue 7 https://doi.org/10.1016/j.polymer.2010.01.067	journal	March 2010
Osmotic pressures of moderately concentrated polydimethylsiloxane solutions Kuwahara, Nobuhiro; Okazawa, Tadahiro; Kaneko, Motozo Journal of Polymer Science Part C: Polymer Symposia, Vol. 23, Issue 2 https://doi.org/10.1002/polc.5070230211	journal	March 2007
Thermodynamics of Swollen Networks As Reflected in Segmental Orientation Correlations Chassé, Walter; Saalwächter, Kay; Sommer, Jens-Uwe Macromolecules, Vol. 45, Issue 13 https://doi.org/10.1021/ma3009004	journal	June 2012
Physical Properties of Polymers Handbook Mark, James E. https://doi.org/10.1007/978-0-387-69002-5	book	January 2007
An investigation of the properties of non-Gaussian poly(dimethylsiloxane) model networks in the swollen state Clarson, S. J.; Galiatsatos, V.; Mark, J. E. Macromolecules, Vol. 23, Issue 5 https://doi.org/10.1021/ma00207a043	journal	March 1990
Bimodal networks and networks reinforced by thein situ precipitation of silica Mark, James E. British Polymer Journal, Vol. 17, Issue 2 https://doi.org/10.1002/pi.4980170211	journal	June 1985

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