阴离子印迹聚合物的制备及其应用研究进展

离子印迹聚合物是利用印迹技术对模板离子进行印迹、聚合进而得到能够选择性吸附该离子的一种特殊聚合物.目前的报道大多是阳离子印迹聚合物,因为阴离子模板结构更复杂多样且电荷尺寸比更小,致使阴离子印迹聚合物的发展相对滞后.为能更有效地指导阴离子印迹聚合物的制备,本文概述了阴离子印迹聚合物的发展现状,介绍了与不同阴离子有相互作用...     

Coupling polymerization of monofunctional allene derivatives with malonates bearing aryl halides moieties via π-allylpalladium complex

A novel polymerization method of allene derivatives with nucleophiles bearing aryl halide moieties (A-B type) is described. By the polymerization of hexylallene with malonates bearing an aryl iodide part, polymers consisting both of internal and exomethylene (exo) double bonds were obtained by mean of the coupling reaction of three different components in high yields. On the other hand, a polymer obtained from phenylallene was selectively composed of internal double bonds (E and Z). By the reaction of hexylallene with a malonate bearing two aryl halide moieties (A-B₂ type), a multibranched polymer was also obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2097–2103, 1997     

Highly phenylated poly(aryl ether phthalazine)s

Two series of novel amorphous poly(aryl ether phthalazine)s have been prepared via an intramolecular ring closure reaction of poly(aryl ether ketone)s (PAEKs) with hydrazine monohydrate. Fluorinated PAEKs, which display solubility in solvents incorporating a ketone functionality such as acetone or ethyl acetate, were converted to poly(aryl ether phthalazine)s to observe if these polymers would display similar solubility characteristics. The poly(aryl ether phthalazine)s have glass transition temperatures in the range of 278–320°C and show 5% weight loss points greater than 500°C in air and nitrogen atmospheres. The fluorinated poly(aryl ether phthalazine)s were not soluble in ketonic solvents. A series of poly(aryl ether phthalazine)s incorporating pendant 2-naphthalenyl moieties has been prepared in an attempt to produce amorphous, thermally stable polymers with high glass transition temperatures. The polymers have glass transition temperatures in the range of 287–334°C and show 5% weight loss points greater than 500°C in air and nitrogen atmospheres. Poly(aryl ether phthalazine)s undergo an exothermic reaction above the glass transition temperature. The major product of this reaction is a rearrangement of the phthalazine moieties to quiazoline moieties, however some crosslinking of the polymers occurs. Cured samples of the poly(aryl ether phthalazine)s show a small increase in the polymer T_g and are insoluble in all solvents tested. © 1996 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 34:1897–1905, 1996     

Impact of the anion on electrochemically doped regioregular and regiorandom poly(3-hexylthiophene)

Chemical and electrochemical doping of π-conjugated polymers is an important aspect in determining the performance and enabling the operation of many organic electronic devices, from organic light emitting diodes and thermoelectrics to organic electrochemical transistors. In both chemical doping and electrochemical doping an ionized dopant or counterion is present along with the doped π-conjugated polymer. This dopant or counterion is not a benign spectator, rather, its presence can significantly impact the optical, electronic, and thermoelectric properties of the resulting material. Here, we investigate how counterion structure impacts the electrochemical doping ability, oxidation potential, ionization energy, and polaron absorbance of regioregular (rr) and regiorandom (rra) P3HT. We find that in most cases the anion has a small effect on the polymer oxidation potential, except for in the case of rr-P3HT with the large tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion. We propose that this large anion is excluded from the crystalline regions and thus the oxidation potential is similar to that of rra-P3HT. The anions also result in significant differences in polaron absorbance and ionization energies, thereby emphasizing the important role of the counterion in determining the optical and electronic properties of doped π-conjugated polymers.     

Preparation of stimulus-responsive,polyfluorene-wrapped carbon nanotubes via palladium cross coupling

Decoration of carbon nanotube surfaces without damaging nanotube optoelectronic properties is an ongoing challenge. Here, we utilize Sonogashira coupling chemistry to decorate the nanotube surface without perturbing optoelectronic properties. Reactive, noncovalently functionalized polymer–nanotube complexes were prepared using a polyfluorene with aryl iodide groups in its side chains. The aryl iodides enable Pd cross coupling between polymer–nanotube complexes and small molecules or polymers derivatized with an alkyne. Modestly efficient coupling was found to occur under dilute conditions at elevated temperatures. Successful coupling between aryl iodide and alkyne partners was observed using infrared spectroscopy via the appearance of carbonyl stretches that originate from covalently linked, carbonyl-containing alkynes, and thermogravimetric analysis was used to measure reaction conversion under various conditions. Grafting of the hydrophobic polymer–nanotube complex with poly(ethylene glycol) enabled the dispersion to be transferred from organic to aqueous solution. This chemistry resulted in no damage to the nanotube sidewall, as evidenced by Raman spectroscopy. The aryl iodide-containing polyfluorene–nanotube complex was also coupled to a photoswitchable alkyne-containing spiropyran moiety and it was found that the photoswitch retained its functionality after coupling to the polymer–nanotube complex. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2723–2729     

Synthesis and Properties of Highly Photoluminescent and Electrochemically Active Polymers Containing 2‐Pyrazoline Units in the Main Chain

Summary: Two new polymers containing 2‐pyrazoline units in the main chain were synthesized for the first time by a Suzuki polycondensation between a 2‐pyrazoline monomer and aryl diboronic esters. The polymers showed high photoluminescence (PL) in both the solution and the solid state; quantum yields of PL in toluene were higher than 76%. Thermogravimetric analysis and cyclic voltammetry showed that the polymers had high thermal stability and good reversibility under electrochemical oxidation.

New polymers ( 2 and 3 ) with strong photoluminescence and good reversibility under electrochemical oxidation were synthesized here.     

Science and technology of perfluorocyclobutyl aryl ether polymers

This article highlights the preparation of perfluorocyclobutyl (PFCB) aryl ether polymers for a multitude of commercial technologies that are of academic and commercial global interest. In this account, the synthesis of various aryl trifluorovinyl ether (TFVE) monomers tailored for specific applications is discussed. The preparation of PFCB aryl ether polymers and their properties is then presented. Topics of PFCB aryl ether polymers and their applications include photonics, polymer light emitting diodes (PLEDs), proton exchange membranes (PEMs) for fuel cells, atomic oxygen (AO) resistant coatings, and hybrid composites. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5705–5721, 2007     

Selective Electrochemical Determination of Salicylic Acid in Wheat Using Molecular Imprinted Polymers

Salicylic acid is a phytohormone, playing crucial roles in signal transduction, crop growth, and development, and defense to environmental challenges. In this study, a highly selective electrochemical sensor was designed and used to determine salicylic acid using molecularly imprinted polymers for recognition. The electrochemical sensor was fabricated via stepwise modification of gold nanoparticle–graphene–chitosan and molecularly imprinted polymers on a glassy carbon electrode. With electrochemical deposition, a gold nanoparticle–graphene–chitosan film was deposited on the glassy carbon electrode and enhanced the sensitivity. Molecularly imprinted polymers with adsorbed template salicylic acid were added to the surface of the modified electrode. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrodes. Salicylic acid in wheat was quantified by the sensor using the molecularly imprinted polymer/gold nanoparticle–graphene–chitosan/glassy carbon electrode. Concentrations of salicylic acid from 5?×?10^?10 to 5?×?10^?5?mol?L^?1 were determined showing that the developed sensor was suitable for the analysis of food.     

Linear A–B and AA–BB polyamides with backbone aryl,alkyl, and alkenyl units

High performance linear AA–BB and A–B polyamides were generated using polymerization schemes that gave polymers in higher yields and having better performance than previous methods. Polymers were characterized with FTIR, solution and solid-state ¹³C-NMR and showed the incorporation of aryl, alkyl, and alkenyl linkages in the polymer backbone. Thermal analysis showed that a significant weight percent of the polymers remained at 1000°C.     

Synthesis of a new class of triphenylamine‐containing poly(ether‐imide)s for electrochromic applications

A novel triphenylamine (TPA)‐containing bis(ether anhydride) monomer, namely 4,4′‐bis(3,4‐dicarboxyphenoxy)triphenylamine dianhydride, was synthesized and reacted with various aromatic diamines leading to a series of new poly(ether‐imide)s (PEI). Most of these PEIs were soluble in organic solvents and could be easily solution cast into flexible and strong films. The polymer films exhibited good thermal stability with glass‐transition temperatures in the range 211–299 °C. The polymer films exhibited reversible electrochemical processes and stable color changes (from transparent to navy blue) with high coloration efficiency and contrast ratio upon electro‐oxidation. During the electrochemical oxidation process, a crosslinked polymer structure was developed due to the coupling reaction between the TPA radical cation moieties in the polymer chains. These polymers can be used to fabricate electrochromic devices with high coloration efficiency, high redox stability, and fast response time. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 825–838     

Block polymers of isocyanates and vinyl monomers by homogeneous anionic polymerization

The “living” polymer method was used to prepare block polymers of vinyl monomers and isocyanates at low temperatures in toluene–tetrahydrofuran mixtures. Vinyl monomers and diisocyanates, which have one hindered isocyanate group, as in 2,4-toluene diisocyanate, form block polymers which contain pendant reactive isocyanate groups. These block polymers can be crosslinked with water, diols, diamines, etc. The polymerization is apparently limited to block polymer formation, since the polyisocyanate anion is incapable of initiating the polymerization of common vinyl monomers.     

Direct vs Indirect Grafting of Alkyl and Aryl Halides

The direct and indirect electrochemical grafting of alkyl and aryl halides (RX, ArX) on carbon, metal and polymer surfaces is examined. Their electrochemical reduction occurs at highly negative potential in organic solvents and very often produces carbanions because the reduction potentials of RX and ArX are more negative than those of their corresponding radicals. Therefore, direct electrografting of alkyl and aryl radicals generated from RX and ArX is not easy to perform. This obstacle is overcome using aryl radicals derived from the 2,6-dimethylbenzenediazonium salt (2,6-DMBD), which do not react on the electrode surface due to their steric hindrance but react in solution by abstracting an iodine or bromine atom from RX (X=I, Br) or ArI to give alkyl or aryl radicals. As a consequence, alkyl and aryl radicals are generated at very low driving force by diverting the reactivity of aryl radicals derived from an aryl diazonium salt; they attack the electrode surface and form strongly attached organic layers. This strategy applies to the chemical modification of polymers (polyethylene, polymethylmethacrylate) by alkyl halides under heating.     

Synthesis,optical and electrochemical properties of arylenevinylene‐based π‐conjugated polymers with imidazolium units in the main chain

Arylenevinylene‐based π‐conjugated polymers containing imidazolium cationic units in the main chain and their model compounds were synthesized and characterized in terms of optical and electrochemical properties. 9,9‐Bisoctylfluorene, 2,5‐bisdodecyloxybenzene, and 3‐dodecylthiophene were introduced as arylene units with different donor characteristics to evaluate the effect on the highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap energy. The UV–vis and fluorescence spectra of cationic polymers and model compounds with iodide counter anion exhibited a significant blue shift with respect to the parent neutral molecules. X‐ray single crystal analysis for model compounds revealed that the effective π‐conjugation length of cationic model compounds decreased compared to the neutral model compounds by means of twisted conformation directed by CH‐π interactions between N‐methyl groups of imidazolium and neighboring aryl units. The cyclic voltammetry measurement suggested the negative shift of LUMO levels by the conversion of imidazole to imidazolium, indicating the electron‐accepting characteristics of cationic imidazolium unit. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Redox monomer ionic liquid based on quaternary ammonium: From electrochemistry to polymer brushes

Bifunctional quaternary ammonium ionic liquid bearing redox and polymerisable units was synthesized. The electrochemical investigations of the ferrocene monomer ionic liquid were performed. Following that, surface-initiated atom transfer radical polymerization (SI-ATRP) was used to build polymer brushes onto the electrode surface. The presence of the Poly(ferrocenyl quaternary ammonium) was evidenced by surface and electrochemical analysis. The latter exhibits high electron transfer rate and the presence of ions within the polymer framework leads to record the attached ferrocenyl redox signal in solution without adding supporting electrolyte. Finally, the wettability of the surface was modulated by electrochemical switch and by anion exchange within the polymer.     

Synthesis,characterization, and properties of regioregular conjugated polymers containing quaterthiophene and an acceptor repeating units

Novel donor–acceptor type polymers consisting of alternating quaterthiophene and an electron withdrawing moiety, pyrazinyl or pyridinyl, have been prepared using Stille coupling approach with moderate yields. The polymers were highly soluble in common organic solvents such as tetrahydrofuran and chloroform. The structure and optical properties of the polymers were characterized by NMR, UV‐vis and fluorescence spectroscopy, and cyclic voltammetry, respectively. The polymer having pyrazine unit exhibited a red‐shift in both absorption and emission in comparison with those analogs containing pyridine because of strong electron withdrawing character of the pyrazinyl group. The polymer containing pyrazinyl as acceptor units also depicted decrease in its optical and electrochemical bandgap relative to those polymers containing 2,5‐ or 2,6‐pyridine moieties. The electrochemical behavior showed facile n‐doping and p‐doping properties of those polymers consisting of alternating quaterthiophene and the acceptor moiety. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2163–2171, 2009     

Elucidation of the electrochemical behavior of phenothiazine-based polyaromatic amines

Polyarlylamines with discrete redox active groups in the polymer backbone represent a promising class of cathode materials for electrical energy storage applications. In this area, our group recently reported a set of phenothiazine-based polymers that exhibit both high capacities and power densities. In order to rationally improve the properties of these electrode materials, a fundamental understanding of their electrochemical properties is indispensable. Herein, we probe the electrochemical behavior of our phenothiazine-based systems by synthesizing small molecule analogs using C–N cross-coupling. Additionally, electropolymerization of a class of these small molecule phenothiazines yields thin films that were then characterized with an electrochemical quartz crystal microbalance. Analysis of these materials provides insights into the number of electrons accessed from each repeat unit in our polymer backbone during electrochemical cycling, as well as counter ion transport dynamics.     

An EQCM study of the electropolymerization of benzene in an ionic liquid and ion exchange characteristics of the resulting polymer film

The direct electropolymerization of benzene dissolved in the ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate was studied at room temperature applying the electrochemical quartz-crystal microbalance technique. Analysis of the damping changes showed that the Sauerbrey equation could be applied for data evaluation. In the polymer, every third to fourth benzene ring carried a positive charge in the oxidized state. During electropolymerization, some ionic liquid was absorbed in the growing polymer. The redox behavior was characterized by wide peaks typical for conducting polymers. Charge neutrality of the polymer during redox cycling was maintained by anion and cation exchange with the ionic liquid. With increasing scan rate, cation exchange became more and more important.     

Synthesis and properties of carbazole‐layered polymers

New aromatic ring‐layered polymers consisting of carbazole as a layered aromatic group and xanthene as a scaffold were designed and synthesized via the Sonogashira–Hagihara coupling reaction. Their optical and electrochemical behaviors were investigated in detail; the results showed that these polymers could be used as hole‐transporting materials. Polymers with nitrobenzene moieties at the polymer chain ends quenched the emission from the layered carbazoles to the nitrobenzene termini; thus, the polymers acted as the molecular wire that transferred photoexcited energy and/or electrons to the polymer termini. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4279–4288, 2009     

Synthesis and properties of anthracene-containing polybenzyls

A number of alternating copolymers containing anthryl and aryl units in the polymer chain have been prepared by Friedel-Crafts arylation of the anthracene (polymer type B) or by condensation of 9,10-bis(chloromethyl) anthracene with opportune aromatic substrates (polymer type A). Polymers of type A were all found to contain 9,10-disubstituted anthracene units, but polymers of type B were found to contain 1,4-disubstituted anthracene units. Structure of the polymers were established through their NMR and ultraviolet spectra, and through analogy with appropriate model compounds. It has been found that the inclusion of anthracene units in the polymer chain yields higher melting and more soluble materials with respect to polybenzyls containing only aryl units. Anthracene units introduce, also, some interesting fluorescence characteristics in the polymers, which show intense emission at about 440 mμ.     

Conjugated polymers based on new thienylene – PPV derivatives for solar cell applications

Two π-conjugated monomers based on bis-(1-cyano-2-thienyl-vinylene)phenylene derivatives were synthesized by Knoevenagel condensation. Both monomers are found to form electroactive polymers upon electrochemical oxidation. The withdrawing effect due to the cyano-substituent allows for the reversible n-doping of the polymer. Thus, the band gap E_g was measured using electrochemical techniques and compared with that obtained by UV–VIS–NIR spectroscopy. Based on the measured band gap of 1.87 and 1.58 eV, these polymers appear to be interesting candidates for solar-cell applications.