Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Abstract

a b s t r a c tPost-polymerization radical bromination of a nanostructured poly(ionic liquid) that selectively introduces a reactive bromo-group onto the polyalkylthiophene backbone is described. Raman and FT-IR spectroscopy proves that the bromine is successfully introduced at the 3-methyl position of the thiophene and that the molecular structure of the polymer remains largely intact with only minimal chain scission detected. FT-IR and Vis-NIR spectroscopy indicates that incorporation of the bromine induces twisting (loss of co-planarity) of the polythiophene backbone. WAXS confirms retention of an ordered lamellar structure with minor lattice spacing contraction. Cyclic voltammetry confirms spectroscopic findings that the bromination reaction yields a stable p-doped polymer. The installed bromine is susceptible to nucleophilic displacement permitting the covalent attachment of other functional molecules, such as a dialkylphosphonate. Elemental analysis of such a transformation established that 100% functionalization can be achieved. These results collectively demonstrate that post-modification of a pconjugated polymer can be used to both tune electronic and photonic properties, as well as install a chemoselective attachment point for the covalent wiring of other molecules.

Preparation of phenyl‐modified natural rubber in latex stage

“…First, the bromination of natural rubber was made with N ‐bromosuccinimide (NBS) under nitrogen atmosphere in dichloromethane. Hydrogen atoms at the allylic position of natural rubber were replaced to bromine atoms, according to the radical mechanism . Second, allylic bromine atoms of the resulting brominated natural rubber were replaced to phenyl groups by the Suzuki‐Miyaura cross‐coupling reaction with phenyl boronic acid in the presence of di‐ μ ‐chloro‐bis [5‐hydroxy‐2‐[1‐(hydroxyimino)‐ethyl] palladium (II) dimer under nitrogen atmosphere in tetrahydrofuran (THF) .…”

“…Hydrogen atoms at the allylic position of natural rubber were replaced to bromine atoms, according to the radical mechanism. [9][10][11] Second, allylic bromine atoms of the resulting brominated natural rubber were replaced to phenyl groups by the Suzuki-Miyaura cross-coupling reaction with phenyl boronic acid in the presence of…”

Encapsulation of ionic liquid BMIm[PF6] within polyurea microspheres

“…Ionic liquids have been immobilized on polymeric materials [21][22][23][24][25][26][27][28][29], porous solids [30][31][32][33][34][35][36][37], and membranes [38][39][40][41]. As opposed to the traditional immobilization techniques, the ionic liquid is usually covalently bonded to the immobilizing matrix, in the encapsulation process, the ionic liquid is physically confined within a shell.…”