Self‐Assembly and Covalent Fixation for Topological Polymer Chemistry

A novel methodology (electrostatic self‐assembly and covalent fixation) has been proposed for designing various nonlinear polymer topologies, including monocyclic and polycyclic polymers, cyclic macromonomers and cyclic telechelics (kyklo‐telechelics), a‐ring‐with‐a‐branch topology polymers and polymeric topological isomers, as well as branched model polymers, such as star polymers and polymacromonomers. Thus, new telechelic polymer precursors having a moderately strained cyclic onium salt group as single or multiple end groups and carrying multifunctional carboxylates as the counterions were prepared through an ion‐exchange reaction. A variety of electrostatic self‐assemblies of these polymer precursors, formed particularly in dilute organic solution, was then subjected to heat in order to convert the ionic interactions into covalent linkages by ring‐opening reaction, and to produce topologically unique, nonlinear polymer architectures in high efficiency.     

Cyclic and linear poly(ferrocenylene alkylene)s synthesized from addition‐condensation polymerization of ferrocene with aldehydes

Oligo‐ and poly(ferrocenylene alkylene)s, [Fe(C₅H_5‐x)(C₅H_5‐y)CHR]_n (x = y = 1 or x = 2, y = 0; R = alkyl, aryl), were synthesized by Lewis acid‐promoted addition‐condensation polymerization of ferrocene with aldehydes. The reaction of alkyl aldehydes, such as n‐hept‐CHO, EtCHO and nBuCHO, with ferrocene yields a mixture of the cyclic and linear poly(ferrocenylene alkylene)s, while aryl aldehyde, such as C₆F₅CHO, CF₃C₆H₄‐4‐CHO and MeC₆H₄‐4‐CHO, forms the linear polymers exclusively. The linear polymer has terminal ? Fe(C₅H₄)(C₅H₅) and ? CH₂Aryl groups, which are characterized by high resolution mass spectroscopy. Results of addition‐condensation polymerization of ferrocenemethanol catalyzed by BF₃ indicate that the propagating polymer of the above addition‐condensation polymerization contains terminal 1‐hydroxyalkyl‐ferrocenylene group, ? Fe(C₅H₄)[C₅H₄{CH(OH)R}]. The trimer prepared from ferrocene and paraformaldehyde dimethylacetal contains 1,1′‐, 1,2‐, and 1,3‐ferrocenylene units, suggesting that the polymers obtained from alkyl and aryl aldehydes are also composed of these structural units. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3627–3635     

Synthesis of Polymeric Topological Isomers through Electrostatic Self‐Assembly and Covalent Fixation with Star Telechelic Precursors

Summary: A pair of macromolecular constitutional isomers having topologically distinctive, dicyclic constructions, that is, θ‐shaped and manacle‐shaped polymers, has been synthesized from a polymer self‐assembly, comprised of three‐armed star poly(tetrahydrofuran) [poly(THF)] having N‐phenylpyrrolidinium salt end groups carrying dicarboxylate counteranions ( 1S / 2d ). The presence of the two constitutional polymeric isomers was confirmed by means of a reversed‐phase liquid chromatography (RPC) technique. Moreover, size exclusion chromatography (SEC) showed that a major component possesses notably larger hydrodynamic volume than the others, and is assignable as a manacle‐shaped isomer while a minor component is assigned as a θ‐shaped isomer. The statistics of the covalent‐linking process of 1S / 2d were consistent with the other experimental results.

An “electrostatic self‐assembly and covalent fixation” process of a trifunctional star‐shaped precursor gives rise to θ‐shaped and manacle‐shaped polymers.     

Twisted Morphologies and Novel Chiral Macroporous Films from the Self‐Assembly of Optically Active Helical Polyphosphazene Block Copolymers

A series of optically active helical polyphosphazene block copolymers of general formula R? [N?P(O₂C₂₀H₁₂)]_n‐b‐[N?PMePh]_m (R‐ 7 a – c ) was synthesized and characterized. The polymers were prepared by sequential living cationic polycondensation of N‐silylphosphoranimines using the mono‐end‐capped initiator [Ph₃P?N?PCl₃][PCl₆] ( 5 ) and exhibit a low polydispersity index (ca. 1.3). The temperature dependence of the specific optical activity ([α]_D) of R‐ 7 a , b relative to that for the homopolymers R‐[N?P(O₂C₂₀H₁₂)]_n (R‐ 8 a ) and the R/S analogues (R/S‐ 7 a , b ), revealed that the binaphthoxy–phosphazene segments induce a preferential helical conformation in the [N?PMePh] blocks through a “sergeant‐and‐soldiers” mechanism, an effect that is unprecedented in polyphosphazenes. The self‐assembly of drop‐cast thin films of the chiral block copolymer R‐ 7 b (bearing a long chiral and rigid R? [N?P(O₂C₂₀H₁₂)] segment) evidenced a transfer of helicity mechanism, leading to the formation of twisted morphologies (twisted “pearl necklace”), not observed in the nonchiral R/S‐ 7 b . The chiral R‐ 7 a and the nonchiral R/S‐ 7 a , self‐assemble by a nondirected morphology reconstruction process into regular‐shaped macroporous films with chiral‐rich areas close to edge of the pore. This is the first nontemplate self‐assembly route to chiral macroporous polymeric films with pore size larger than 50 nm. The solvent annealing (THF) of these films leads to the formation of regular spherical nanostructures (ca. 50 nm), a rare example of nanospheres exclusively formed by synthetic helical polymers.     

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Herein the stereoselective two‐step synthesis of pure exo‐5‐trimethylsilylnorbornene is reported. The monomer proved to be highly reactive in both metathesis and addition polymerization. ROMP polymerization was catalyzed by the first‐generation Grubbs catalyst. High‐molecular‐weight saturated addition polymers were prepared using nickel or palladium complexes as precatalysts and Na⁺[B(3,5‐(CF₃)₂C₆H₃)₄]⁻ and/or MAO as cocatalysts. The obtained addition polynorbornenes are highly gas permeable and microporous materials possessing large free volume and BET surface area (up to 540 m²/g). The influence of the substituent orientation (exo‐ vs. exo‐/endo‐mixture) on polymer properties was established. The metathesis polymer based on exo‐isomer exhibits 1.5‐ to 2‐fold increase of permeability coefficients for all gases in comparison to the similar polymer based on the mixture of exo‐ and endo‐isomers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1234–1248     

Controlling supramolecular polymerization through multicomponent self‐assembly

The self‐assembly into supramolecular polymers is a process driven by reversible non‐covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli‐responsive properties: (1) end‐capping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of self‐assembly kinetics of synthetic supramolecular systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 34–78     

Computational study of tautomerism and aromaticity in mono‐ and dithio‐substituted tropolone

Keto‐enol tautomerism in mono‐ and dithio‐substituted analogs of tropolone was investigated using electronic structure computations. Seven structural isomers of C₇H₆OS and four of C₇H₆S₂ were optimized fully in gas phase at HF and B3LYP theoretical levels in combination with the 6‐311++g** basis set, as well as with the CBS‐QB3 and G3 methods. To examine the effects of an aqueous solvent on tautomeric equilibrium constants, each species was optimized in water using the self‐consistent reaction field polarizable continuum model at HF/6‐311++g** and B3LYP/6‐311++g** model chemistries. In both phases it was found that the enol forms were significantly more stable with respect to electronic energy and Gibbs free energy compared to the keto isomers, and outnumbered the keto species by several orders of magnitude. This was understood on the basis of elementary Hückel theory and the 4n + 2 rule, and supported by nucleus independent chemical shifts computations of NMR chemical shifts in these seven membered cyclic systems. © 2012 Wiley Periodicals, Inc.     

Synthesis and Characterization of Poly(chiral methylpropargyl ester)s Carrying Azobenzene Moieties

Novel chiral methylpropargyl esters bearing azobenzene groups, namely, 4‐[4′‐(benzyloxy)phenylazophenyl]‐ carbonyl‐(S)‐1‐methylpropargyl ester ( e ), 4‐[4′‐(n‐butyloxy)phenylazophenyl]carbonyl‐(S)‐1‐methylpropargyl ester ( f ), 4‐[4′‐(n‐hexyloxy)phenylazophenyl]carbonyl‐(S)‐1‐methylpropargyl ester ( g ), and 4‐[4′‐(n‐octyloxy)phenylazo‐ phenyl]carbonyl‐(S)‐1‐methylpropargyl ester ( h ) were synthesized and polymerized with Rh⁺(nbd)[η⁶‐C₆H₅B^?‐ (C₆H₅)₃] (nbd=norbornadiene) catalyst to give the corresponding polymers with moderate molecular weights (M_n=8.4×10³–15.7×10³) in good yields (76%? –?91%). The structures of polymers were illustrated by IR and NMR spectroscopies. Polymers were soluble in comment organic solvents including toluene, CHCl₃ CH₂Cl₂, THF, and DMSO, while insoluble in diethyl ether, n‐hexane and methanol. Large optical rotations of polymer solutions demonstrated that all the polymers take a helical structure with a predominantly one‐handed screw sense in organic solvents.     

Synthesis and properties of blue light‐emitting,silicon‐containing,regio‐ and stereoregular conjugated polymers

This article concerns the hydrosilylation polyaddition of 1,4‐bis(dimethylsilyl)benzene ( 1 ) with 4,4′‐diethynylbiphenyl, 2,7‐diethynylfluorene ( 2b ), and 2,6‐diethynylnaphthalene with RhI(PPh₃)₃ catalyst. Trans‐rich polymers with weight‐average molecular weights (M_w's) ranging from 19,000 to 25,000 were obtained by polyaddition in o‐Cl₂C₆H₄ at 150–180 °C, whereas cis‐rich polymers with M_w's from 4300 to 34,000 were obtained in toluene at 0 °C–r.t. These polymers emitted blue light in 4–81% quantum yields. The cis polymers isomerized into trans polymers upon UV irradiation, whereas the trans polymers did not. The device having a layer of polymer trans‐ 3b obtained from 1 and 2b demonstrated electroluminescence without any dopant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2774–2783, 2004     

Synthesis,characterization, and properties of polyurethanes containing 1,4:3,6‐dianhydro‐D‐sorbitol

Two‐ and three‐component polyurethanes containing 1,4:3,6‐dianhydro‐D ‐sorbitol (isosorbide) derived from glucose were synthesized using n‐BuSn(?O)OH·H₂O as a catalyst, and the thermal properties (T_g, T_d) of the polymers were investigated by differential scanning calorimetry and thermogravimetric analysis. We carried out molds for polyurethanes, the molds of polyurethanes were obtained. The dynamic mechanical analyzes showed that the storage modulus values of the three‐component polymers were constant to a higher temperature than those of the two‐component polymers. The storage moduli (E′), loss moduli (E″), and values of tan δ for the polymers were obtained. The rigidity of three‐component polymers was increased by the introduction of bisphenol A and diphenylmethane group to two‐component polymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6025–6031, 2009     

Synthesis of macrocycles by the ring‐crossover reaction of a cyclic dithioester

The ring‐crossover polymerization of cyclic dithioester 1 was performed in the presence of quaternary onium salts as catalysts at 70–150 °C for 24 h in NMP. It was found that predictable cyclic polymers with the same repeating structures as 1 were obtained with M_ns in the range between 700 and 3,500, quantitatively. It was observed that intermolecular and intramolecular thioester‐exchange reactions proceeded between cyclic monomer 1 and resulting cyclic polymers under thermodynamic control to give a lower‐molecular‐weight cyclic polymer with a lower polydispersity ratio (M_n = 2,400, M_w/M_n = 1.70). © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 680–687, 2007     

Polymerization and copolymerization of functionalized 2‐alkoxy‐1‐methylenecyclopropanes to form new polymers having alkoxy substituents

The polymers with functionalized alkoxy groups and with narrow molecular weight distribution (M_w/M_n < 1.12) are obtained from the living polymerization of 2‐alkoxy‐1‐methylenecyclopropanes using π‐allylpalladium complex, [(PhC₃H₄)Pd(μ‐Cl)]₂, as the initiator. The polymers with oligoethylene glycol groups in the alkoxy substituent are soluble in water, and hydroboration of the C?C double bond and ensuing addition of the OH groups to C?N bond of alkyl isocyanate produce the polymers with urethane pendant groups. The reaction decreases solubility of the polymer in water significantly. Di‐ and triblock copolymers of the 2‐alkoxy‐1‐methylenecyclopropanes are prepared by consecutive addition of the two or three 2‐alkoxy‐1‐methylenecyclopropane monomers to the Pd initiator. The polymers which contain both hydrophobic butoxy or tert‐butoxy group and hydrophilic oligoethylene glycol group dissolve in water and/or organic solvents, depending on the substituents. The ¹H NMR spectrum of poly( 1a ‐b‐ 1h ) (? (CH₂C(?CH₂)CHOBu)_n? (CH₂C(?CH₂)CH(OCH₂CH₂)₃OMe)_m? ) in D₂O solution exhibits peaks because of the butoxy and ?CH₂ hydrogen in decreased intensity, indicating that the polymer forms micelle particles containing the hydrophilic segments in their external parts. Aqueous solution of the polymer with a small amount of DPH (DPH = 1,6‐diphenyl‐1,3,5‐hexatriene) shows the absorbance due to DPH at concentration of the polymer higher than 5.82 × 10^?5 g mL^?1. Other block copolymers such as poly( 1b ‐b‐ 1h ) and poly( 1a ‐b‐ 1g ) also form the micelles that contain DPH in their core. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 959–972, 2009     

"Directed" assembly of metallacalix[n]arenes with pyrimidine nucleobase ligands of low symmetry: metallacalix[n]arene derivatives of cis-[a2M(cytosine-N3)2]2+ (M=Pt(II), Pd(II); n=4 and 6)

Pyrimidine (pym) ligands with their two endocyclic N‐donor atoms provide 120° angles for molecular constructs, which, with the 90° angle metal fragments cis‐a₂M^II (M=Pt, Pd; a=NH₃ or a₂=diamine), form cyclic complexes known as metallacalix[n]arenes (with n=3, 4, 6, 8, …?). The number of possible isomers of these species depends on the symmetry of the pym ligand. Although highly symmetrical (C_2v) pym ligands form a single linkage isomer for any n and can adopt different conformations (e.g., cone, partial cone, 1,3‐alternate, and 1,2‐alternate in the case of n=4), low‐symmetry pym ligands (C_s) can produce a higher number of linkage isomers (e.g., four in the case of n=4) and a large number of different conformers. In the absence of any self‐sorting bias, the number of possible species derived from a self‐assembly process between cis‐a₂M^II and a C_s‐symmetrical pym ligand can thus be very high. By using the C_s‐symmetric pym nucleobase cytosine, we have demonstrated that the number of feasible isomers for n=4 can be reduced to one by applying preformed building blocks such as cis‐[a₂M(cytosine‐N3)₂]ⁿ⁺ or cis‐[a₂M(cytosinate‐N1)₂] (for the latter, see the accompanying paper: A. Khutia, P. J. Sanz Miguel, B. Lippert, Chem. Eur. J. 2011 , 17, DOI: 10.1002/chem.2010002723) and treating them with additional cis‐a₂M^II. Moreover, intramolecular hydrogen‐bonding interactions between the O2 and N4H₂ sites of the cytosine ligands reduce the number of possible rotamers to one. This approach of the “directed” assembly of a defined metallacalix[4]arene is demonstrated.     

Designing polymer topology by electrostatic self‐assembly and covalent fixation

A novel methodology (electrostatic self‐assembly and covalent fixation) has been proposed for designing unusual polymer topologies such as star polymers, polymacromonomers, dumbbell‐shaped polymers as well as model network polymers. Thus new telechelic polymers having moderately strained cyclic onium salt group as single or both end groups were prepared and subjected to an ion‐exchange reaction to introduce multifunctional carboxylate anions as a counter‐anion. The electrostatically self‐assembled products were then subjected, either directly or after subsequent manipulation, to heat treatment to convert the ionic interaction into the covalent linkage by the ring‐opening reaction to produce a variety of topologically unique polymer architectures in high yields.     

Synthesis,light emission,and photovoltaic properties of perylene‐containing polyacetylenes

Perylene (Py)‐containing polyacetylenes with different skeleton structures ? [HC?C(C₆H₄)CO₂? Py]_n? (P 1 ), ? [HC?C(CH₂)₈CO₂? Py]_n? (P 2 ), and ? {[(C₆H₅) C?C(CH₂)₉NH₂]? co? [(C₆H₅)C?C(CH₂)₉? Py]}_n? (P 3 ) are synthesized in satisfactory yields by Rh‐catalyzed polymerization (for P 1 and P 2 ) and polymer reaction (for P 3 ). All the polymers are soluble and possess high molecular weights (M_w up to 2.8 × 10⁵). Their structures and properties are characterized and evaluated by IR, NMR, UV, TGA, PL, and photovoltaic (PV) analyses. The polymers are thermally stable, losing little of their weights when heated to 330 °C. When their solutions are irradiated, their perylene pendants emit intense red fluorescence at 610 nm. PV cells with a configuration of ITO/PEDOT:PSS/polymer/LiF/Al are fabricated, which show maximum current density of 10.3 μA/cm². The external quantum efficiency is sensitive to the polymer structure, with P 3 exhibiting the highest value of 0.23%. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2025–2037, 2008     

Micron‐granula polyolefin with self‐immobilized nickel and iron diimine catalysts bearing one or two allyl groups

Self‐immobilized nickel and iron diimine catalysts bearing one or two allyl groups of [ArN?C]₂(C₁₀H₆)NiBr₂ [Ar = 4‐allyl‐2,6‐(i‐Pr)₂C₆H₂] ( 1 ), [ArN?C(Me)][Ar′N? C(Me)]C₅H₃NFeCl₂ [Ar = Ar′ = 4‐allyl‐2,6‐(i‐Pr)₂C₆H₃, Ar = 2,6‐(i‐Pr)₂C₆H₃, and Ar′ = 4‐allyl‐2,6‐(i‐Pr)₂C₆H₃] were synthesized and characterized. All three catalysts were investigated for olefin polymerization. As a result, these catalysts not only showed high activities as the catalyst free from the allyl group, such as [ArN?C]₂C₁₀H₆NiBr₂ (Ar = 2,6‐(i‐Pr)₂C₆H₂)], but also greatly improved the morphology of polymer particles to afford micron‐granula polyolefin. The self‐immobilization of catalysts, the formation mechanism of microspherical polymer, and the influence on the size of the particles are discussed. The molecular structure of self‐immobilized nickel catalyst 1 was also characterized by crystallographic analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1018–1024, 2004     

Nanostructured polymetallaynes of controlled length: Synthesis and characterization of oligomers and polymers from 1,1′‐bis‐(ethynyl)4,4′‐biphenyl bridging Pt(II) or Pd(II) centers

The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu₃)₂ (C?C? C₆H₄? C₆H₄? C?C? )]_n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR ³¹P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007     

High‐molar‐mass polypropene with tunable elastic properties by hafnocene/borate catalysts

Elastic polypropene has gained growing industrial and academic interest as a thermoplastic elastomer. In this study, “rac”‐ and “meso”‐dimethylsilyl(3‐benzylindenyl)(2‐methylindenyl)hafnium dichloride complexes (Hfr and Hfm, respectively), activated with [NHMe₂Ph][B(C₆F₅)₄]/triisobutyl aluminum, were used in propene polymerization. Using these catalyst systems, we obtained polymers with high molar masses, up to 550 kg/mol, and moderate isotacticities between 34 and 52%. By varying the polymerization conditions, we could modify the polymer microstructure and molar mass. ¹³C NMR was used to calculate the polymer pentad sequence distributions. The crystalline parts of the polymers were analyzed with the differential scanning calorimetry successive self‐nucleation and annealing (SSA) technique. The SSA thermograms revealed that Hfr produced polypropene with a more uniform lamellar structure than Hfm. The mechanical properties were tested with dynamic mechanical analysis creep‐recovery tests. In the series, the polymers with the lowest isotacticities and therefore lowest crystallinities showed the best elastic properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4743–4751, 2006     

Helical polyacetylenes carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy moieties: Their synthesis,properties, and function

2,2,6,6‐Tetramethyl‐1‐piperidinyloxy (TEMPO)‐ and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy (PROXYL)‐containing (R)‐1‐methylpropargyl TEMPO‐4‐carboxylate ( 1 ), (R)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 2 ), (rac)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 3 ), (S)‐1‐propargylcarbamoylethyl TEMPO‐4‐carboxylate ( 4 ), and (S)‐1‐propargyloxycarbonylethyl TEMPO‐4‐carboxylate ( 5 ) (TEMPO, PROXYL) were polymerized to afford novel polymers containing the TEMPO and PROXYL radicals at high densities. Monomers 1–3 and 5 provided polymers with moderate number‐average molecular weights of 8200–140,900 in 49–97% yields in the presence of (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃], whereas 4 gave no polymer with this catalyst but gave polymers possessing low M_n (3800–7500) in 56–61% yield with [(nbd)RhCl]₂‐Et₃N. Poly( 1 ), poly( 2 ), and poly( 4 ) took a helical structure with predominantly one‐handed screw sense in THF and CHCl₃ as well as in film state. The helical structure of poly( 1 ) and poly( 2 ) was stable upon heating and addition of MeOH, whereas poly( 4 ) was responsive to heat and solvents. All of the free radical‐containing polymers displayed the reversible charge/discharge processes, whose capacities were in a range of 43.2–112 A h/kg. In particular, the capacities of poly( 2 )–poly( 5 )‐based cells reached about 90–100% of the theoretical values regardless of the secondary structure of the polymer, helix and random. Poly( 1 ), poly( 2 ), and poly( 4 ) taking a helical structure exhibited better capacity tolerance towards the increase of current density than nonhelical poly( 3 ) and poly( 5 ) did. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5431–5445, 2007     

Electrochemical polymerization of aniline in the SDS/n‐C5H11OH/H2SO4(aq) lyotropic liquid crystal

Electrochemical polymerization of aniline was performed by the method of ultramicroelectrode cyclic voltammetry in the lamellar liquid crystal and hexagonal liquid crystal of SDS/n‐C₅H₁₁OH/H₂SO₄(aq) system. The results indicate that the electrochemical polymerization of aniline can be catalyzed by the SDS/n‐C₅H₁₁OH/H₂SO₄(aq) lyotropic liquid crystal. The polymerization potential of aniline is smaller in the lyotropic liquid crystal system than that in the 0.10 mol L?1 sulfuric acid solution. The catalytic efficiency and polymerization rate of aniline increase with the n‐pentanol content, but decrease with the increase of the SDS content or [PhNH₂/H₂SO₄(aq)] content. Moreover, the catalytic efficiency of the lamellar liquid crystal exceeds that of the hexagonal liquid crystal in the SDS/n‐C₅H₁₁OH/H₂SO₄(aq) system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2388–2394, 2006