Mixed (electronic and ionic) conductive solid polymer matrix, 1. Synthesis and properties of poly(2,5,8,11,14,17,20,23‐octaoxapentacosyl methacrylate)‐block‐poly(4‐vinylpyridine)

Abstract

Poly(2,5,8,11,14,17,20,23-octaoxapentacosyI methacrylate)-block-poly(4-vinylpyridine) semicomb polymers were synthesized using anionic living polymerization techniques. The polymers are white, powdery materials and were characterized by 'H and '3C nuclear magnetic resonance spectroscopy and gel-permeation chromatography. The polymers display monomodal molecular weight distributions which are relatively narrow. The block copolymers show microphase separation as indicated by the presence of two glass transition temperatures (Tg), a soft (oxyethylene) phase Tg is observed between -60°C and -45°C and a hard (4-vinylpyridine) phase Tg is observed between 135 "C and 150°C. The soft oxyethylene phase has been doped with LiC10, to obtain ionic conductors with electrical conductivities around 5 .S . cm-' at 25 "C and the hard 4-vinylpyridine phase has been complexed with 7,7,8,8-tetracyano-1,4-quinodimethane (TCNQ, 2,5-cyclohexadiene-t,4-diylidenedimalonitrile) to obtain electronic conductivities around S 1 cm-' at 25 "C. The mixed (electronic and ionic) conductivities are intermediate between the ionic and electronic conductivities. Higher electronic conductivities ( = 10 -5 S . cm-' at 30°C) are obtained for the polycation TCNQ-/TCNQo complexes.

Mixed (ionic and electronic) conductive solid polymer matrix. Synthesis and characterization of homopolymers of 3-(2,5,8,11,14,17,20,23-octaoxyhexadodecyl)thiophene and copolymers with 3-methylthiophene

“…The homopolymer, P[3-(OHDT)], of the macromonomer and copolymers with 3-methylthiophene have been prepared by oxidative coupling using FeCl 3 in CHCl 3 . The homopolymer, P[3-(OHDT)], of the macromonomer and copolymers with 3-methylthiophene have been prepared by oxidative coupling using FeCl 3 in CHCl 3 .…”

“…[3,13] The frequency dependence of the sample impedances were measured with a Hewlett Packard 4192A Impedance Analyzer over a range of 5 Hz to 13 MHz. A polymer pellet (13 mm diameter) sandwiched between two copper electrodes was packed in a sealed cell under a dry nitrogen atmosphere.…”

“…A small amount of phosphorous pentoxide was placed on the bottom of the cell to protect the sample from moisture. [3] [3,13] The frequency dependence of the sample impedances were measured with a Hewlett Packard 4192A Impedance Analyzer over a range of 5 Hz to 13 MHz.…”

Complexation between hydrogensulfated fullerenol and poly(4-vinylpyridine)

“…P4VPy has already been commercially used as an electroactive material in solid-state electrochemical cells in pacemakers 22) . Conductive polymer complexes have also been formed using P4VPy as an electron-donating polymer and I 2 or tetracyanoquinodimethane (TCNQ) as an electron acceptor [23][24][25] . P4VPy can also form interpolymer complexes with acidic polymers such as poly(monomethyl itaconate) 26) , poly(ethylene-comethacrylic acid) 27) , poly(2-acrylamido-2-methylpropanesulfonic acid) 28) and poly(p-vinylphenol) 29) .…”

Characteristics of gel electrolytes formed by self-aggregating comb-shaped polyethers with end-functionalised side chains

“…An alternative, in some regards more useful, way is to employ aggregating or self-assembling polymers to form physically cross-linked polymer electrolyte systems. This has for example been successfully achieved using self-assembling block copolymers with ionophilic blocks, usually of poly(ethylene oxide) (PEO), to complex the salt and facilitate the ion conduction, and ionophobic blocks which induce a phase-separated system with mechanical strength [4][5][6][7][8][9][10]. Basically, these systems resist flow because this would mean mixing the ionophobic blocks with the ionophilic blocks, and vice versa, which is thermodynamically unfavourable.…”