Polypyrroles block copolymers

Gursel, A Alkan, S Toppare, L Yagci, Y. ImmobiUzation of Invertase and Glucose Oxidase in Conducting H-lype Polysiloxane/Polypyrrole Block Copolymers. Reactive and Functional Polymers, 2003 57, 57-65. 

Kapui et al. prepared a novel type of polypyrrole films [168]. The film was impregnated by spherical styrene-methacrylic acid block copolymer micelles with a hydrophobic core of 18 nm and a hydrophilic corona of 100 nm. The properties of the micelle-doped polypyrrole films were investigated by cyclic voltammetry and SECM. It was found that the self-assembled block copolymer micelles in polypyrrole behave as polyanions and the charge compensation by cations has been identified during electrochemical switching of the polymer films. 

I Kapui, RE Gyurcsanyi, G Nagy, K Toth, M Area, E Area. Investigation of styrene-methacrylic acid block copolymer micelle doped polypyrrole films by scanning electrochemical microscopy. J Phys Chem B 102 9934-9939, 1998. 

S.T. Selvan, T. Hayakawa, M. Nogami, and M. Moller, Block copolymer mediated synthesis of gold quantum dots and novel gold-polypyrrole nanocomposites, J. Phys. Chem. B, 103, 7441-7448 (1999). 

Beattie, D., Wong, K.H., Williams, C., Poole-Warren, L.A., Davis, T.P., Bamer-Kowollik, C., et al. Honeycomb-structured porous films from polypyrrole-containing block copolymers prepared via RAFT polymerization as a scaffold for cell growth. Biomacromolecules 7, 1072-1082 (2006)... 

Our interest is to develop MIEC block copolymers with microphase separated structures such that the electronic and ionic phases are in intimate contact at the few hundred angstrom level. We believe that such intimate contact between the two phases will result in functional polymers capable of very fast responses, e.g., in sensors and MEMS devices. A synthetic muscle functions by converting chemical energy into mechanical energy [5]. A biopolymer strip capable of carrying out this function consists of a polyethylene layer, a thin gold layer, and a polypyrrole layer immersed in an electrolyte solution. Oxidation of the polypyrrole results in... 

Electrical properties have been reported on numerous carbon fiber-reinforced polymers, including carbon nanoflber-modified thermotropic liquid crystalline polymers [53], low-density polyethylene [54], ethylene vinyl acetate [55], wire coating varnishes [56], polydimethyl siloxane polypyrrole composites [50], polyacrylonitrile [59], polycarbonate [58], polyacrylonitrile-polycarbonate composites [58], modified chrome polymers [59], lithium trifluoromethane sulfonamide-doped polystyrene-block copolymer [60], boron-containing polyvinyl alcohols [71], lanthanum tetrafluoride complexed ethylene oxide [151, 72, 73], polycarbonate-acrylonitrile diene [44], polyethylene deoxythiophe-nel, blends of polystyrene sulfonate, polyvinyl chloride and polyethylene oxide [43], poly-pyrrole [61], polypyrrole-polypropylene-montmorillonite composites [62], polydimethyl siloxane-polypyrrole composites [63], polyaniline [46], epoxy resin-polyaniline dodecyl benzene sulfonic acid blends [64], and polyaniline-polyamide 6 composites [49]. 

Random copolymers have been prepared by electropolymerization of a mixture of terthienyl derivates and pyrrole [348]. Otherwise, a thiophene-pyrrole block copolymer showing electrical and electrochemical properties intermediate between those of polypyrrole... 

Another widely used approach is the in situ polymerization of an intractable polymer such as polypyrrole onto a polymer matrix with some degree of processibil-ity. Bjorklund [30] reported the formation of polypyrrole on methylcellulose and studied the kinetics of the in situ polymerization. Likewise, Gregory et al. [31] reported that conductive fabrics can be prepared by the in situ polymerization of either pyrrole or aniline onto textile substrates. The fabrics obtained by this process maintain the mechanical properties of the substrate and have reasonable surface conductivities. In situ polymerization of acetylene within swollen matrices such as polyethylene, polybutadiene, block copolymers of styrene and diene, and ethylene-propylene-diene terpolymers have also been investigated [32,33]. For example, when a stretched polyacetylene-polybutadiene composite prepared by this approach was iodine-doped, it had a conductivity of around 575 S/cm and excellent environmental stability due to the encapsulation of the ICP [34]. Likewise, composites of polypyrrole and polythiophene prepared by in situ polymerization in matrices such as poly(vinyl chloride), poly(vinyl alcohol), poly(vinylidine chloride-( o-trifluoroethylene), and brominated poly(vi-nyl carbazole) have also been reported. The conductivity of these composites can reach up to 60 S/cm when they are doped with appropriate species [10]. 

Some specific recent applications of the GC-MS technique to various types of polymers include the following PE [49,50], poly(l-octene) [51], poly(l-decene) [51], poly(l-dodecene) [51], 1-octene-l-decene-l-dodecene terpolymer [51], chlorinated polyethylene [52], polyolefins [53, 54], acrylic acid methacrylic acid copolymers [55], polyacrylates [56], styrene-butadiene and other rubbers [57-59], nitrile rubber [60], natural rubbers [61, 62], chlorinated natural rubber [63, 64], polychloroprene [65], PVC [66-68], silicones [69, 70], polycarbonates [71], styrene-isoprene copolymers [72], substituted PS [73], polypropylene carbonate [74], ethylene-vinyl acetate copolymers [75], Nylon [76], polyisopropenyl cyclohexane a-methyl styrene copolymers [77], m-cresol-novolac epoxy resins [78], polymeric flame retardants [79], poly(4-N-alkyl styrenes) [80], polyvinyl pyrrolidone [81], vinyl pyrrolidone-methyl acryloxysilicone copolymers [82], polybutylcyanoacrylate [83], polysulfide copolymers [84], poly(diethyl-2-methacryloxy)ethyl phosphate [85], ethane-carbon monoxide copolymers [86], polyetherimide [87], bisphenol A [88], ethyl styrene [89], styrene-isoprene block copolymer [89], polyvinyl alcohol-co-vinyl acetate [90], epoxide thiol [91], maleic acid-propylene copolymer [92], P-hydroxy butyrate-P-hydroxy valerate copolymer [93], polycaprolactams [39,94], PS [95,96], polypyrrole [95,96], polyhydroxy alkanoates [97], poly(p-chloromethyl) styrene [81], polybenzooxazines and siloxy substituted polyoxadisila-pentanylenes [98,99] poly benzyl methacrylates [100], polyolefin blends after ageing in soil [101] and polystyrene peroxide [43]. 

Some measurements of this property have been made in a range of electrically conducting polymers. These include epoxy resin/polyaniline-dodecylbenzene sulfonic acid blends [38], polystyrene-black polyphenylene oxide copolymers [38], semiconductor-based polypyrroles [33], titanocene polyesters [40], boron-containing polyvinyl alcohol [41], copper-filled epoxy resin [42], polyethylidene dioxy thiophene-polystyrene sulfonate, polyvinyl chloride, polyethylene oxide [43], polycarbonate/acrylonitrile-butadiene-styrene composites [44], polyethylene oxide complexes with sodium lanthanum tetra-fluoride [45], chlorine-substituted polyaniline [46], polyvinyl pyrolidine-polyvinyl alcohol coupled with potassium bromate tetrafluoromethane sulfonamide [47], doped polystyrene block polyethylene [38, 39], polypyrrole [48], polyaniline-polyamide composites [49], and polydimethyl siloxane-polypyrrole composites [50]. 

This chapter is divided into two main parts polythiophene copolymers and polypyrrole copolymers. Each part reviews the random copolymerization of the heterocyclic monomer and important derivatives, principally those with substituents at the 3-position of thiophene and at the 1- and 3-positions of pyrrole. Alternating, block and graft copolymers are covered in both segments. Because applications of conducting polymers are reviewed in Volume 4, only applications unique to specify copolymers are covered here. In addition, a few theoretical studies dealing with conducting copolymers are reviewed. 

This improvement in stability of polypyrrole with copolymerization permitted the construction of a Schottky barrier type diode of this copolymer and indium metal [106]. The copolymer was heated in order to stabilize the electrical characteristics of the device before deposition of the blocking electrode and the contact between the metal and copolymer was probed by XPS [107]. 

Cyclic voltammetry of the copolymer shows three anodic peaks, two matching the oxidation potentials of the parent homopolymers and a third which is intermediate. Authors attributed the data to the formation of blocks of polypyrrole and polythiophene cormected by blocks of random alternating groups of pyrrole and bithiophene. Increasing the amount of bithiophene in the copolymer produced a strong drop in the final conductivity of the materials, from 17 S cm at 1 mol% to I S cm at 14 mol%. 

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