Self‐Healing Metallo‐Supramolecular Amphiphilic Polymer Conetworks

Abstract

The current challenge in self‐healing materials resides in the design of materials which exhibit improved mechanical properties and self‐healing ability. The design of phase‐separated nanostructures combining hard and soft phases represents an attractive approach to overcome this limitation. Amphiphilic polymer conetworks are nanostructured materials with robust mechanical properties, which can be tailored by tuning the polymer composition and chemical functionality. This article highlights the design of phase‐separated nanostructured polymers from metallo‐supramolecular amphiphilic polymer conetworks, and their application for self‐healing surfaces. The synthesis of poly(N‐(pyridin‐4‐yl)acrylamide)‐l‐polydimethylsiloxane polymer conetworks from the poly(pentafluorophenyl acrylate)‐l‐polydimethylsiloxane activated ester is presented. Loading of ZnCl2 salt into the phase‐separated polymer conetwork strengthens the network by cross‐linking the poly(N‐(pyridin‐4‐yl)acrylamide) phases, while offering reversible interactions needed for self‐healing ability.

Scratch‐Healing Surface‐Attached Coatings from Metallo‐Supramolecular Polymer Conetworks

“…( Figure ) The surface analysis of the PPFPA‐ l ‐PDMS coatings by AFM height and phase analysis revealed nanophase morphologies typical of APCNs with larger interconnected PDMS spherical nanodomains of 26 ± 2 nm in diameter, dispersed in a PPFPA matrix ( Figure a,b) compared to our previous study where smaller PDMS nanodomains of 10 nm in diameter were observed. [ 21 ]…”

“…The concentration of the Zn(II) ions of 8.5 ± 0.1 wt% was determined by inductively coupled plasma mass spectrometry analysis and corresponded to a molar ratio of PNP4EA to Zn(II) close to 2:1, which is similar to that reported for the metallo ‐polymer conetwork films. [ 21 ] The cross‐section of the polymer coating was measured by optical microscope and revealed that loading of Zn(II) resulted in an increase of the thickness from 34.5 ± 1.6 µm (PNP4EA‐ l ‐PDMS) to 47 ± 1 µm (PNP4EA‐Zn(II)‐ l ‐PDMS) as a result of the complexation of Zn(II) ions by the PNP4EA phases (Figure S5, Supporting Information).…”

“…Recently, self‐healing metallo ‐supramolecular polymer conetwork films were reported and the impact of the metal complexes on the recovery of mechanical properties after healing has been demonstrated. [ 21 ] Herein, the self‐healing ability is optimized for surface‐attached metallo ‐polymer conetwork coatings.…”

Nanoconfined Crosslinked Poly(ionic liquid)s with Unprecedented Selective Swelling Properties Obtained by Alkylation in Nanophase-Separated Poly(1-vinylimidazole)-l-poly(tetrahydrofuran) Conetworks

“…Nanoconfined material structures, including polymers as well, due to the wide range of unique structural features, properties, and effects arising under nanocompartmentalized conditions, have created significant worldwide interest over the last couple of years (see e.g., references [ 1 , 2 , 3 , 4 , 5 , 6 ] and references therein). The recently emerged polymer conetworks, especially amphiphilic conetworks (APCNs), composed of covalently or supramolecularly bonded, otherwise immiscible, hydrophilic and hydrophobic polymer chains, belong to such nanophase-separated materials with mutually nanoconfined macromolecular components [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ]. Considering that polymers containing imidazole rings, which also play a pivotal role in the major biopolymers and compounds of living organisms, such as DNA, RNA, proteins, enzymes, hormones, vitamins, etc., provide various advantageous properties, like water solubility, strong metal ion coordinating ability, protonation, and alkylation possibilities, we have recently explored the synthesis, nanophasic structure, and properties of poly(1-vinylimidazole)- l -poly(tetrahydrofuran) (PVIm- l -PTHF) and poly(1-vinylimidazole)- l -poly(propylene...…”

Small‐Angle X‐Ray Scattering Measurements on Amphiphilic Polymer Conetworks Swollen in Orthogonal Solvents

“…[ 6 ] They can also be used as membranes with pH [ 7 ] and thermally responsive swelling [ 7e,8 ] as well as for chiral separation, [ 9 ] and even APCNs with controlled ion conductivity [ 10 ] and self‐healing properties have been reported. [ 11 ] Another important field of APCNs is their use as activating carriers for enzymes. [ 12 ] For example, Bruns et al.…”