Reactive and Functional Polymers (v.65, #1-2)

Preface by Karel Jeřábek (vii).

Calendar (I).

Contents (xi-xii).

A novel chiral 1,2-diamine monomer (S,S)-12 has been synthesized and copolymerized with styrene to give cross-linked polymer. After deprotection of the tert-butoxycarbonyl groups, polymer-supported chiral 1,2-diamine (S,S)-P was obtained. The primary 1,2-diamine moieties on the polymer have been allowed to form the complex with RuCl2/(S)-BINAP. The polymeric chiral complex was used as a catalyst of asymmetric hydrogenation of aromatic ketones to yield the corresponding secondary alcohols in quantitative conversion with high level of enantioselectivity. The polymeric catalyst was recycled several times without any loss of the catalytic activity.
Keywords: Polymer-support; Asymmetric hydrogenation; Ketone; Chiral 1,2-diamine; BINAP;

Linear and crosslinked copolymers of p-tert-butylcalix[4]arene derivatives and styrene: New synthetic approaches to polymer-bound calix[4]arenes by Ana R. Mendes; Carla C. Gregório; Patrícia D. Barata; Alexandra I. Costa; José V. Prata (9-21).
As an extension of our previous studies concerning the free radical copolymerisation of 25,26,27-tripropoxy-28-(4-vinyl-benzyloxy)-p-tert-butylcalix[4]arene (3) with styrylic monomers, we report herein on the synthesis and characterisation of new terpolymers derived from 3, styrene and divinylbenzene, having nominal crosslinking degrees ranging from 4% to 40% wt. The terpolymers exhibited good thermal stabilities (DSC) and were prepared in good yields. Depending on the reaction conditions (dilution degree and aqueous phase to porogen ratio), materials with identical nominal crosslinking but otherwise differentiated morphologies and swelling abilities were obtained.In a related study, the radical polymerisation of styrene was carried out in the presence of a novel calix[4]arene derivative 4, bearing two distal benzyl–vinyl groups in the lower rim. It is shown that, albeit the presence of two phenolic groups within the calixarene moiety which could have functioned as inhibitors of the free radical polymerisation, the macrocycle was able to take part in the copolymerisation reaction, yielding new soluble and crosslinked polymers. In both cases, no pendant vinyl groups were found in the polymeric materials. The probable mechanisms underlying their formation are discussed.
Keywords: Calixarene; Radical polymerisation; Cyclopolymerisation; Vinyl; Styrene; Linear; Crosslinked;

Highly soluble poly(2,7-carbazolenevinylene) for thermoelectrical applications: From theory to experiment by Isabelle Lévesque; Xing Gao; Dennis D. Klug; John S. Tse; Christopher I. Ratcliffe; Mario Leclerc (23-36).
A new highly soluble derivative of poly(2,7-carbazolenevinylene) was synthesized, bearing alkyl side chains in the 3,6 positions. The polymer synthesized was characterized by optical, electrochemical and electrical measurements. The stability towards chemical doping at room temperature is investigated. The Seebeck coefficients at room temperature are measured for different doping levels and compared to poly(3-decylthiophene). At high doping level, the Seebeck coefficient is around 200–250 μV/K, which is one order of magnitude higher than poly(3-decylthiophene). At low doping level, the Seebeck coefficient reaches 600 μV/K. The carbazolenevinylene polymer is not very conductive, the highest conductivity obtained being 5 × 10−3 S/cm. The electronic band structure and the Seebeck coefficients at room temperature are calculated and compared to experimental results.
Keywords: Conjugated polymers; Carbazole; Thermoelectricity; Seebeck coefficient; Band structure calculations;

4-Vinylbenzyl chloride (VBC) based water-in-oil-in-water emulsions with 85% pore volume and 70% VBC in organic phase were prepared and polymerised by free radical polymerisation. Porous spherical particles of diameters between 50 and 150 μm were obtained and their morphological structure and reactivity studied by FTIR spectroscopy, elemental analysis, optical microscopy, scanning electron microscopy and mercury intrusion porosimetry. Strong influence of the suspension stabiliser, namely poly(N-vinylpyrrolidone) (PVP), on the particle form was found. Diameters of spherical polymers particles depend on the PVP concentration, being larger with the lower concentration of PVP. Reactivity of novel supports was demonstrated by the reactions with piperidine, piperazine, tris(hydroxymethyl)methylamine and tris(2-aminoethyl)amine, all yielding corresponding amine derivatives.
Keywords: Multiple emulsions; Polymer supports; 4-Vinylbenzyl chloride; Solid phase synthesis; High internal phase emulsions;

Poly(tetrafluoroethylene-co-perfluorovinylether)-g-polystyrene sulfonic acid (PFA-g-PSSA) membranes were prepared by radiation-induced grafting of styrene onto PFA films using a simultaneous irradiation technique and a subsequent sulfonation in a chlorosulfonic acid/dichloroethane mixture. The PFA films were exposed to γ irradiation doses of 50–200 kGy at a dose rate of 10 kGy/h. The physico-chemical properties of the PFA-g-PSSA membranes such as the degree of grafting, ion exchange capacity, water uptake and tensile strength were evaluated. The structure variations after the grafting and sulfonation were investigated using FTIR-ATR spectroscopy. Differential scanning calorimetry and thermogravimetric analysis have been used to study the thermal decomposition and the melting behavior of the grafted PFA films. The as-prepared PFA-g-PSSA membranes in this work showed a good combination of a high ion exchange capacity (1.8–3.25 meq/g), acceptable water uptake (40–70 wt%), low thickness and volume expansion and/or contraction.
Keywords: PFA; Radiation-grafting; Sulfonation; Fuel cell;

Heterogeneous membranes filled with hypercrosslinked microparticle adsorbent by J. Hradil; V. Krystl; P. Hrabánek; B. Bernauer; M. Kočiřík (57-68).
Synthesis of hypercrosslinked microparticles is described and the effect of reaction conditions on adsorbent properties is discussed. Heterogeneous membranes based on hypercrosslinked microparticle adsorbent with a poly(phenylene oxide) binder were prepared and tested for separation of hydrogen from a isobutane/hydrogen mixture. The separation process was characterized by parameters, such as diffusion flux, permeability, and selectivity. The prepared membranes were superior to the homogeneous ones in permeability and to zeolite-filled membranes in selectivity. Selectivity reached values of about 540 in H2/isobutane separation.
Keywords: Heterogeneous membranes; Hypercrosslinked adsorbent; Microparticles; Polymer binder; Poly(phenylene oxide); Hydrogen/isobutane separation; Separation characteristics;

Nanocomposites based on titanium dioxide and polythiophene: Structure and properties by Quoc-Trung Vu; Martin Pavlik; Niels Hebestreit; Ursula Rammelt; Waldfried Plieth; Jiri Pfleger (69-77).
A composite of polythiophene (PTh) and nanoscopic titanium dioxide (TiO2), possessing core-shell structure, was prepared via oxidative polymerization of thiophene by iron (III) chloride in the presence of TiO2 particles. The morphology of the obtained composite particles was studied by transmission electron microscopy (TEM), proving the core-shell structure of the prepared nanocomposite. The chemical structure of the composites was investigated by Raman spectroscopy. The electrophoretic deposition (EPD) technique was used as a method to prepare composite layers on various conducting substrates (platinum and ITO plate). The characteristics of the composite layer after EPD were studied by electrochemical methods. The photoelectrical properties of PTh and TiO2 in the nanocomposites were studied as well. In the photoelectrochemical spectra (depending on the applied potential), the characteristic anodic peak of TiO2 at λ  = 340 nm and cathodic peak of PTh around λ  = 530 nm were observed. A bandgap energy, E g  = 1.95 eV and a direct electron transition of PTh were found. A cathodic peak in the photocurrent spectra was detected unexpectably also around 340 nm, and ascribed to the photoelectrical activity of the TiO2 core. The redox processes in PTh were investigated via cyclic voltammetry (CV) and electrochemical impedance microscopy (EIS).
Keywords: Polythiophene; Titanium dioxide; Nanocomposites; Electrophoretic deposition; Photoelectrochemical spectra;

Electronic processes in end-functionalized oligomeric poly(diphenylvinylene)s by Jiří Pfleger; Martin Pavlík; Jiří Vohlídal (79-91).
The photoluminescence and photoelectrical properties of soluble poly(diphenylvinylene)s (PDV) of the mean number-average degree of polymerization ranging from 7 to 9 with main chains end-capped with: (i) diphenylmethylene (PDV-P), (ii) phenylcarbonyl (PDV-C), and (iii) fluorene-9,9-diyl (PDV-F) groups are reported. The introduced groups were found to affect the decay path of photogenerated excitons significantly: PDV-P shows the medium-intensity photoluminescence in the blue spectral region and poor photoconductivity decreasing about one order of magnitude when going from the excitation wavelength λ exc of 254–366 nm; PDV-C exhibits fluorescence quenching but the photoconductivity 10 times as high as that of PDV-P, which, however, decreases about almost two orders of magnitude when changing λ exc from 254 to 366 nm; PDV-F shows strong photoluminescence and high photoconductivity which does not decrease significantly if λ exc is changed from 254 to 366 nm. The observed behavior of PDV-F shows that not always a strong photoluminescence should be accompanied with a weak photoconductivity, which is explained by a formation of aggregates in PDV-F, into which excitons are effectively transferred. This trapping results in a prolonged lifetime of excitons and, consequently, in an increase in the charge carrier formation at high electric field. On the other hand, the aggregates also act as traps hindering the charge carrier transport in PDV-F. Since PDV-C also shows a reasonable photoelectrical sensitivity at low electric fields, it was tested as an active material for photovoltaic cells. The obtained parameters of the ITO/PDV-C/Al sandwich cell (illumination with white light of the intensity ca. 10 mW cm−2): short-circuit current I sc  = 2 × 10−10  A, open circuit voltage U oc  = 0.5 V and fill factor FF = 0.5 provided a rather discouraging value of the power efficiency of about 10−7.
Keywords: Conjugated polymers; Charge carrier photogeneration; Fluorescence; Photoconductivity; Polydiphenylacetylene; Polyacetylenes; Photovoltaic cells;

New oxidation–reduction polymers on the basis of pyridine nitriles by E.E. Ergozhin; B.A. Mukhitdinova; V.V. Shaligina; B.Zh. Shekeeva; K.M. Sartbaeva (93-101).
Oxidation–reduction polymers have been obtained by polymerization of pyridine nitriles and their derivatives in the presence of Friedel–Crafts catalysts and complex catalysts. The influence of the nature of the substituents in pyridine nitriles, the nature of catalyst, temperature and time of the process upon the conversion of monomers has been discussed. The data on the sorption ions of transition metals have been presented. The principal physical–chemical, acidic–basic and oxidation–reduction properties of the synthesized macromolecules have been determined.
Keywords: Oxidation–reduction ion exchangers; Pyridine nitriles; Oxidation–reduction properties; Sorption;

New oxidation–reduction monomers and polymers on the basis of monoethanolamine vinyl ether, allylamine and some quinones by E.E. Ergozhin; B.A. Mukhitdinova; S.A. Shoinbekova; B.M. Nuranbaeva; Zh.I. Moldagazieva; G.N. Zhunusova (103-112).
The paper presents the results of investigations directed to synthesis and study of novel oxidation–reduction monomers on the basis of monoethanolamine vinyl ether, allylamine and quinones of different structure. It has been shown that in contrast to monoethanolamine vinyl ether and allylamine its quinoid derivatives polymerize.
Keywords: Monoethanolamine vinyl ether; Allylamine; Quinones; Oxidation–reduction monomers (polymers);

New method of the synthesis of aminophenolic ionites and study of ion sorption of non-ferrous metals and iodine by E.E. Ergozhin; B.A. Mukhitdinova; A.O. Baikonurova; G.A. Usolzeva; B.E. Begenova (113-119).
A simple method of obtaining of aminophenolic resins by condensation of dioxybenzene with hexamethylenediamine in the presence of formaldehyde was developed. The structure and properties of the reaction products, principal physical–chemical and sorption characteristics have been studied.
Keywords: Dioxybenzenes; Hexamethylenediamine; Formaldehyde; Sorption; Heavy non-ferrous metals; Iodine;

Poly(acrylamide) is grafted onto cross-linked poly (4-vinyl pyridine) (P4-VP) resin “Reillex 425”. Its quaternization with potassium chloroacetate results in cross-linked poly (4-vinyl pyridine) having carboxymethyl pyridinium groups. This resin is grafted with acrylamide after redox initiation through the carboxyl groups with cerium ammonium nitrate.The resulting resin with 111.7 wt% of poly(acrylamide) grafts is a high capacity (3.36 mmol g−1) mercury specific sorbent.Experiments performed under identical conditions with some other ions such as Zn(II), Pb(II), Fe(III) and Cd(II) showed that those metal ions are not sorbed by the resin.Flexible graft chains of poly(acrylamide) provide nearly homogeneous reaction conditions in mercury uptake. Regeneration of the mercury loaded polymer can be achieved by acetic acid treatment.
Keywords: Mercury uptake; Poly(vinyl pyridine) resin; Poly(acrylamide) graft polymer; Redox polymerization;

The preparation and the application of grafted polytetrafluoroethylene fiber as a cation exchanger for adsorption of heavy metals by Jun Fu Wei; Zhi Peng Wang; Jing Zhang; Yue Ying Wu; Zheng Pu Zhang; Chun Hua Xiong (127-134).
A novel type of weakly acidic cation exchange fiber have been prepared by 60Co irradiation grafting with acrylic acid onto the polytetrafluoroethylene (PTFE) fiber. The exchange capacity of the grafted fiber is 3.06 mmol/g. The pH titration curve of the grafted fiber showed there is a sudden jump when pH is round 6–10, and the acidity of the grafted fiber is stronger than that of commercial weakly acidic exchange D-152 resin. The grafted fiber showed the excellent selectivity of static and dynamic adsorption for Cu2+, La3+ and Pb2+ when Mg2+, Ca2+, Cr3+, Co2+, Ni3+, Cu2+, Ag+, La3+, Pb2+ were coexisted. The grafted fiber could be regenerated completely with almost equimolar diluted hydrochloric acid.
Keywords: PTFE fiber; Irradiation; Ion exchanger; Heavy metals;

New functional resins with long functional ligands were synthesised by modification of poly(vinylbenzylchloride–acrylonitryle–divinylbenzene) matrix with ethylenediamine, bis(aminopropyl)amine, bis(aminohexyl)triamine or tris(2-aminoethyl)amine. The derivatives were reacted with S-methylthiourea to obtain resins with 2.8–5.0 mmol of amino group per 1 g of dry resin. Sorption efficiency of resin towards Au(III), Pt(IV), Pd(II) chlorocomplexes was determined in a batch mode multicomplexes solutions of Cu(II), Ni(II) and Fe(III) chlorides in 0.1–3 M HCl. The sorption capacity of gold, platinum and palladium from 0.1 M hydrochloric solutions reaches the value of 190, 245 and 280 mg/g, respectively. Recovery of noble metals reveals average of 95% from mulitcomponent solutions.
Keywords: Vinylbenzyl chloride–acrylonitryle–divinylbenzene copolymers; Gold; Platinum and Palladium sorption; Selective resins;

Reaction of diallylamine with crosslinked terpolymer beads of glycidyl metacrylate–methyl methacrylate–ethylene glycol dimethacrylate yields corresponding polymers with diallylamino functions (2.4 mmol g−1). Cis-dihydroxylation of the allyl groups with hydrogen peroxide, in presence of OsO4 catalyst yields polymer supported amino-bis(cis-propane 2,3-diol) functions with 81.7% of conversion yields. The resulting polymer resin having vicinal cis-diol functions is a high capacity (1.77 mmol g−1) boron-specific sorbent and useful for extraction of of trace boric acid (105.1 ppm) from aqueous solutions in about 20 min.
Keywords: Boron removal; Cis-dihydroxylation; Glycidyl methacrylate; Polymeric sorbent;

Dimerization of 2-methyl-1-butene and 2-methyl-2-butene mixture using Amberlyst 35, Amberlyst 15, Amberjet 1500H, Purolite CT-175 and Purolite CT-275 as catalysts was carried out in a discontinuous stirred tank reactor at 353 K in methanol and ethanol presence in a molar ratio isoamylenes/alcohol = 9. Amberlyst 35 was found to be the most active resin. Alcohol presence appeared to improve the selectivity for diisoamylenes: no significant amounts of trimers, tetramers or cracking products were obtained in the studied conditions. Almost all the alcohol react in the first reaction stages to form ether. Both alcohols gave the same correlation between isoamylenes conversion and diisoamylenes selectivity: as conversion increases, selectivity increases, diisoamylenes yield and isoamylenes conversion being lower in ethanol than in methanol presence. 2,3,4,4-tetramethyl-1-hexene, 3,4,4,5-tetramethyl-2-hexene and 3,4,5,5-tetramethyl-2-hexene were the main dimers obtained.
Keywords: Ion-exchange resin; 2-Methyl-1-butene; 2-Methyl-2-butene; Dimerization; Diisoamylene;

Series of acrylic resins with aminoguanidyl groups were prepared by aminolysis of nitrile groups in acrylonitrile, vinyl acetate and divinylbenzene terpolymer using aminoguanidine bicarbonate and hydrazine and subsequent substitution with thiourea/ethyl iodide (TEI) mixture. Complexation of the carriers with copper(II) acetate leads to the heterogenized catalysts with immobilized copper. Their catalytic activity was measured in the model oxidation reaction of hydroquinone (H2Q) to p-benzoquinone (Q) using hydrogen peroxide. The catalysts were tested in the same reaction in the presence of ionic liquid [bmim]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate). Under optimal conditions the main product, i.e. p-benzoquinone was obtained after 60 min with 66% yield. The catalytic activity of the catalysts depends on Cu(II) loading and concentration of ion-exchange groups after sorption. Selectivity increases slightly in the presence of ionic liquid.
Keywords: Aminoguanidyl ligands; Copper(II) catalyst; Hydroquinone oxidation; Ionic liquid;

Immobilization of methyltrioxorhenium onto tertiary amine and pyridine N-oxide resins by Lina María González R.; Aída L. Villa de P.; Consuelo Montes de C.; Georges Gelbard (169-181).
Novel heterogeneous aminated polystyrene and polyacrylate resins and vinylpyridine copolymerized with methylmethacrylate and buthylmethacrylate, were synthesized, characterized and used as supports for MTO immobilization. FTIR, UV–VIS, chemical analysis and 13C NMR indicate that tertiary amine and pyridine N-oxides can act as ligands for MTO anchoring onto polymeric resins. The amount of rhenium incorporated and the interaction between N and Re varied with the ligand type and the polymer. MTO immobilized on oxidized supports was proner to leaching than non-oxidized supports during α-pinene epoxidation with hydrogen peroxide. MTO supported on copolymers were more effective for the latter reaction than MTO supported on tertiary amines or commercial polyvinylpyridine.
Keywords: Methyltrioxorhenium; Polyvinylpyridine; Heterogenization; α-Pinene; Catalytic oxidation; Hydrogen peroxide;

Soil reclamation with ion exchange resins by Mariola Chomczyńska; Lucjan Pawłowski; Vladimir Soldatov (183-190).
In the studies, ion exchange substrates prepared from new (standard) and spent ion exchange resins were used as fertilisers introduced into sand that served as a model of degraded soil. The obtained results showed a strong effect of the additions of standard ion exchange substrates on grass yield. It progressively increased with the increase of substrate fraction in the sand at its low content (up to 5–7%). One percent additions only of ion exchange substrates into sand increased plant yield from three to nine times. It was also noticed that an addition of one volume percent of the substrate brought the fertility of sand to that of commercially available garden soil. Results of the experiments with spent ion exchangers exhibited their fertiliser utility as an ion exchange substrate (the Mp substrate) and as monoionic forms containing potassium, nitrate and phosphate ions (the NPK monoionic forms). The plant yield obtained on sand enriched with the Mp substrate or with the NPK monoionic forms was from 1.5 to 4.5 times higher than that obtained on sand alone. At the same time the boost to growth to be attributed to the introduction of the standard substrate into sand was from two to four times greater than that caused by an addition of the Mp substrate or the NPK monoionic forms. The higher efficacy of the standard substrate compared to that of the Mp resulted from greater potassium and phosphorus contents in that substrate. The lower plant biomass on sand fertilised with the NPK monoionic forms compared to that obtained on sand enriched with the standard substrate was caused by a lower content of nitrogen, potassium and phosphorus and a lack of calcium, magnesium and sulphur in the mixture of the NPK forms.
Keywords: Ion exchangers; Ion exchange substrate; Soil reclamation; Plant cultivation;

Presented posters (191-194).