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Structure-Property Relationship between Hard Segments of Shape Memory Polyurethane Copolymers and Interchain Hydrogen
Yuliia Didovets1,2, Mateusz Z Brela1
1Molecular Spectroscopy Group, Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, PL30387 Cracow, Poland.
The Journal of Physical Chemistry. B
|September 25, 2025
Summary
Shape memory polyurethane copolymers rely on interchain hydrogen bonds within Hard Segments for their properties. Hexamethylene diisocyanate (HDI) and diphenylmethane-4,4'-diisocyanate (MDI) based segments exhibit the strongest hydrogen bonds, enhancing material performance.
Area of Science:
- Polymer Science
- Materials Science
- Computational Chemistry
Background:
- Shape memory polymers (SMPs) are gaining attention for their unique properties.
- Interchain hydrogen bonds in Hard Segments are crucial for the shape memory effect in polyurethane copolymers.
Purpose of the Study:
- To comprehensively describe the interchain interactions network of Hard Segments in SMP polyurethane copolymers.
- To investigate the influence of different chemical compositions on hydrogen bond characteristics.
Main Methods:
- Utilized *ab initio* molecular dynamics to simulate the reorganization of interchain hydrogen bonds.
- Employed interaction energy decomposition (ETS) and IR spectrum analysis to determine hydrogen bond character and strength.
- Studied model Hard Segments based on hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), toluene-2,4-diisocyanate (TDI), and diphenylmethane-4,4'-diisocyanate (MDI).
Main Results:
- HDI- and MDI-based Hard Segments formed the strongest interchain hydrogen bonds.
- TDI-based Hard Segments exhibited the weakest interactions.
- HMDI-based Hard Segments demonstrated intermediate interaction strength.
Conclusions:
- Established a direct correlation between the character of interchain hydrogen bonds in Hard Segments and the thermal and mechanical properties of polyurethane copolymers.
- The findings provide insights into tailoring SMP properties through control of Hard Segment chemistry and hydrogen bonding.
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