High-Strength, Self-Healing Copolymers of Acrylamide and Acrylic Acid with Co(II), Ni(II), and Cu(II) Complexes of 4'-Phenyl-2,2':6',2″-terpyridine: Preparation, Structure, Properties, and Autonomous and pH-Triggered Healing

Polymers (Basel). 2024 Nov 9;16(22):3127. doi: 10.3390/polym16223127.

Abstract

The utilization of self-healing polymers is a promising way of solving problems associated with the wear and tear of polymer products, such as those caused by mechanical stress or environmental factors. In this study, a series of novel self-healing, high-strength copolymers of acrylamide, acrylic acid, and novel acrylic complexes of 4'-phenyl-2,2':6',2″-terpyridine [Co(II), Ni(II), and Cu(II)] was prepared. A systematic study of the composition and properties of the obtained polymers was carried out using a variety of physicochemical techniques (elemental analysis, gel permeation chromatography (GPC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR), ultraviolet-visible spectroscopy (UV-vis), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), confocal laser scanning microscopy (CLSM), and tensile testing). All metallopolymer samples exhibit autonomous intrinsic healing along with maintaining high tensile strength values (for some samples, the initial tensile strength exceeded 100 MPa). The best values of healing efficiency are possessed by metallopolymers with a nickel complex (up to 83%), which is most likely due to the highest lability of the metal-heteroatom coordination bonds. The example of this system shows the ability to re-heal with negligible deterioration of the mechanical properties. The possibility of tuning the mechanical properties of self-healing films through the use of different metal ions has been demonstrated.

Keywords: metal acrylates; metal-containing monomers; metallopolymers; self-healing; supramolecular polymers; terpyridine-containing polymers.

Grants and funding

This work has been carried out in accordance with the state tasks, state registration 124013000722-8 (FFSG-2024-0007), 124013000757-0 (FFSG-2024-0010) and 124020800013-7 (FFSG-2024-0017) using the equipment of the Multi-User Analytical Center of FRC PCP and MC RAS.