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. 2025 Jul 16;17(14):1951.
doi: 10.3390/polym17141951.

Furan-Urethane Monomers for Self-Healing Polyurethanes

Polina Ponomareva  1 , Zalina Lokiaeva  1 , Daria Zakharova  2 , Ilya Tretyakov  1 , Elena Platonova  1 , Aleksey Shapagin  3 , Olga Alexeeva  4 , Evgenia Antoshkina  5 , Vitaliy Solodilov  1 , Gleb Yurkov  1 , Alexandr Berlin  1
Affiliations

Furan-Urethane Monomers for Self-Healing Polyurethanes

Polina Ponomareva et al. Polymers (Basel). .

Abstract

The repair efficiency of various self-healing materials often depends on the ability of the prepolymer and curing agent to form mixtures. This paper presents a synthesis and study of the properties of modified self-healing polyurethanes using the Diels-Alder reaction (DA reaction), obtained from a maleimide-terminated preform and a series of furan-urethane curing agents. The most commonly used isocyanates (4,4'-methylene diphenyl diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and hexamethylene diisocyanate (HDI)) and furan derivatives (furfurylamine, difurfurylamine, and furfuryl alcohol) were used as initial reagents for the synthesis of curing agents. For comparative analysis, polyurethanes were also obtained using the well-known "traditional" approach-from furan-terminated prepolymers based on mono- and difurfurylamine, as well as furfuryl alcohol and the often-used bismaleimide curing agent 1,10-(methylenedi-1,4-phenylene)bismaleimide (BMI). The structure and composition of all polymers were studied using spectroscopic methods. Molecular mass was determined using gel permeation chromatography (GPC). Thermal properties were studied using TGA, DSC, and TMA methods. The mechanical and self-healing properties of the materials were investigated via a uniaxial tensile test. Visual assessment of the completeness of damage restoration after the self-healing cycle was carried out using a scanning electron microscope. It was shown that the proposed modified approach helps obtain more durable polyurethanes with a high degree of self-healing of mechanical properties after damage.

Keywords: Diels–Alder reaction; polyurethane; remendability; self-healing.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
Schematic representation of the proposed approach.
Figure 2
Figure 2
Furan–urethane monomers.
Scheme 1
Scheme 1
Synthesis of PU-DA polymers: A—traditional approach, B—modified approach.
Figure 3
Figure 3
Schematic view of a reversible covalent and physical bonds formed during the curing of a prepolymer with furan–urethanes: (I)—reversible bonds based on tetrafuranurethanes; (II)—reversible bonds based on difuranurethanes.
Figure 4
Figure 4
Spectra: (a) NMR spectra of PU-H2, prepolymer and curing agent; (b) NMR spectra of tetrafuranic and difuranic PU; (c) IR spectra of PU-H2, prepolymer and curing agent.
Figure 5
Figure 5
TGA (left) and DTG (right) curves of PU samples: (a) modified (PU-H-series); (b) traditional.
Figure 6
Figure 6
DSC curves of PU samples: (a) modified (PU-H-series); (b) traditional (solid lines—first heat, dashed lines—second heat).
Figure 7
Figure 7
Thermomechanical curves for PU-DA samples: (a) modified (PU-H-series); (b) traditional; (c) curves of the first derivative ε’(T) of PU-DA samples.
Figure 8
Figure 8
Load diagrams for PU-DA: (a) original and healed PU-H (PU-H-series); (b) original and healed PU-DA traditional.
Figure 9
Figure 9
SEM-images of PUs: (a) modified (PU-T2); (b) traditional (PU-(NFu)2).
See this image and copyright information in PMC

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