Solid-state NMR Applications in Polymers

We summarize the solid-state NMR techniques used by our group to characterize the structures and dynamics of a variety of polymer systems.

1. Characterization of crosslinking density and fraction of defects in polymer networks.

Techniques: Low-field 1H multiple-quantum (MQ) NMR

Refs: Saalwaechter, K. et al. J. Chem. Phys. 2003, 119, 3468.

Applications:

Rubbers (Macromolecules, 2013, 46,1841; Macromolecules, 2024, 57, 11727 )

Hydrogels (Macromolecules, 2017, 50, 9340; Macromolecules, 2025, 58, 149)

Polyurethane ( J. Phys. Chem. B, 2014, 118, 1126; Polymer, 2019, 163, 154)

Supramolecular elastomers (Macromolecules, 2020, 53, 5937; Angew. Chem. Int. Ed. 2025, 64, e202422104

2. Distinguish different components with obvious mobility contrast in multiphase polymers

Techniques: T2-relaxometry based NMR methods

Refs:  Saalwaechter, K. et al. Solid State Nucl. Magn. Reson. 2015, 72, 50

Applications:

Polymer Nanocomposites (J. Phys. Chem. C, 2014, 118, 5606）

Adhesives (Macromolecules, 2026, 59, 802)

Polyurethanes (J. Phys. Chem. B, 2014, 118, 1126)

Slide-ring elastomer (Macromolecules, 2025, 58, 9171)

3. High-resolution structure and dynamic characterization of multiphase polymers

Techniques: 1D 13C and 2D 13C-1H HETCOR experiments based on CP, RINEPT and NOE

Refs: Zhang RC et al. J. Magn. Reson. 2016, 266, 59;  (1D CP-RINEPT, CP-NOE)

                                   J. Magn. Reson. 2019, 309, 106615; (2D 13C/1H HETCOR with CP and RINEPT)

                            J. Phys. Chem. C, 2022, 126, 13311; (1D CPPI-f-NOE, 2D HETCOR with CP and NOE)

                          J. Magn. Reson. 2023, 357, 107597 (1H T₁ and T_1p with CP and RINEPT)

Applications:

Supramolecular elastomers ( Angew. Chem. Int. Ed. 2025, 64, e202422104)

Adhesives (Macromolecules, 2026, 59, 802)

Polyurethanes (Polymer, 2018, 148, 127)

4. Fast-field-cycling NMR to study polymer dynamics

Techniques: Fast-field-cycling NMR

Refs: Roessler, E. et al. Prog. Nucl. Magn. Reson. Spectrosc. 2012, 63, 33-64; 高分子通报, 2025, 38, 244

Applications:

Polymer blends (Macromolecules, 2025, 58, 3478)

5. Molecular Interactions by 2D homo- and heteronuclear Correlation NMR spectroscopy 

Techniques: 2D 1H/1H multiple-quantum/single-quantum (MQ/SQ) correlation, or 2D 13C/1H HETCOR

Refs: Zhang RC et al. J. Magn. Reson. 2015, 252, 55-66  (1H/1H correlation)

                                   Solid State Nucl. Magn. Reson. 2021, 114, 101734 (1H DQ/SQ correlation)

                                  J. Phys. Chem. C, 2020, 124, 26332 (1H TQ/SQ correlation)

Applications:

Polymer blend (Macromolecules, 2025, 58, 3478) (1H/1H SQ/SQ)

Silk/cellulose blend (J. Phys. Chem. B, 2017, 121, 5944)  (13C/1H HETCOR)

UPy quadruple hydrogen bonds (Macromolecules, 2019, 52, 5014) (1H/1H DQ/SQ)

metal coordination in elastomers (Macromol. Rapid Commun. 2025, 46, e00601) (1H/1H DQ/SQ)