New fibrous carboxyl cation exchangers FIBAN were synthesized by the method of graft copolymerization to polypropylene staple fibers of acrylic acid and various bifunctional comonomers (divinylbenzene – DVB, ethyleneglycoldimethacrylate – EGDM, methylene-bis-acrylamide – MBAA). Sorption properties of the fibers towards cations of heavy and non-ferrous metals (Cо2+, Ni2+, Zn2+, Cd2+, Cu2+ и Pb2+) were studied on the model solutions in the dynamic regime. The dynamic activity of the crosslinked sorbents towards Cu2+ and Pb2+ ions is higher compared to fibrous analogues FIBAN Х-1, FIBAN Х-2, FIBAN К-6М, FIBAN К-5, VION КN-1. The best sorbent for lead ions between the crosslinked fibers is the fiber with EGDM. The fiber with MBAA has a higher affinity towards the cations of Ni2+, Zn2+, Cd2+ and Cа2+, which increases with the increasing of the degree of crosslinking by MBAA. Studying the fibers by the methods of Fourier-transform IR-spectroscopy, scanning electron microscopy, analyzing of the chemical oxygen demand in water extracts and determination of the equivalent moisture capacity coefficient coefficient demonstrated that the crosslinking by MBAA provides a stable structure of the sorbent. The high stability of the crosslinked structure combined with the high ion exchange capacity near 7 mEq/g and dynamic activity towards the cations of Pb2+, Zn2+, Cd2+ и Cа2+ makes the fibrous carboxyl sorbent with MBAA safe and perspective for drinking water purification.
In this work, a study was made of the sorption of boric acid from aqueous solutions by fibers of the FIBAN brand (Institute of Physical Organic Chemistry of the National Academy of Sciences of Belarus, Belarus), which have functional amino groups in their structure. The possibility of using FIBAN A-1, A-5, and A-6 fibrous materials for the extraction of boron compounds from aqueous solutions has been established. According to the sorption kinetic curves, a high rate of sorption of boric acid by high- and low-basic anion exchangers was noted. Also, some equilibrium characteristics of analyte sorption by the studied sorbents are estimated in the work. A complex multivariant mechanism of sorption of boric acid by FIBAN A-1 and A-5 fibers was revealed, which includes both chemisorption uptake of H 3 BO 3 by amino groups of sorbents in the range of low concentrations and the possibility of formation and fixation of polyborates in the phase of the ion exchanger in the range of high concentrations (superequivalent sorption).
В работе проведено исследование сорбции борной кислоты из водных растворов волокнами марки ФИБАН ("Институт физико-органической химии Национальной академии наук Беларуси", Беларусь), имеющими в своем строении функциональные аминогруппы. Установлена возможность использования волокнистых материалов ФИБАН А-1, А-5 и А-6 для извлечения соединений бора из водных растворов. Согласно кинетическим кривым сорбции отмечена высокая скорость сорбции борной кислоты высоко- и низкоосновными анионообменниками. Также в работе оценены некоторые равновесные характеристики сорбции аналита исследуемыми сорбентами. Выявлен сложный многовариантный механизм поглощения борной кислоты волокнами ФИБАН А-1 и А-5, который включает как хемосорбционное поглощение H 3 BO 3 аминогруппами сорбентов в области низких концентраций, так и возможность образования и закрепления в фазе ионообменника полиборатов в области высоких концентраций (сверхэквивалентная сорбция).
A new one-stage method has been developed for the production of aminocarboxyl ion exchanger FIBAN K-6 based on polyacrylonitrile fibre using inexpensive and accessible reagents. The new aminocarboxyl ion exchanger FIBAN K-6M with controlled swelling in water was obtained from the fibrous ion exchanger FIBAN K-6. The sorption properties of FIBAN K-6 and K-6M fibres from multicomponent solutions were studied. The advantages of these ion exchangers are shown not only in comparison with other aminocarboxyl ion exchangers FIBAN K-3 and K-5, but also with the best sorbents of heavy metal ions FIBAN X-1 and X-2 with iminodiacetate groups. It has been established that the mechanical properties of the fibrous cation exchanger FIBAN K-6M allow to process it into non-woven material or yarn with high yield and use it in the form of cartridges in water purification filters.
A synthesis method of new fibrous anion exchangers with strong base groups has been developed. The synthesis was carried out by alkylation of weakly basic anion exchangers based on polyacrylonitrile fiber using two alkylating agents: epichlorohydrin and ethylene chlorohydrin. The influence of the reaction conditions on the physicochemical properties of new anion exchangers was investigated. The synthesis parameters were determined: the molar ratio of “amino groups: alkylating agent”, the concentration of the alkylating agent, the reaction time and temperature – to obtain anion exchangers with maximum exchange capacity for strong base groups. New strongly basic fibers possess satisfactory mechanical properties allowing their processing into various textile forms.
The sorption of sulfur dioxide from the air by the fibrous anion exchangers containing amino groups of different structure and basicity has been comparatively investigated. The most effective sorbents of sulfur dioxide are the anion exchangers with ternary amino groups, which have a high exchange capacity (more than 5 meq/g) and additionally contain secondary amino groups. The anion exchangers with high-base amino groups absorb sulfur dioxide at low relative humidity (30 %) but have low dynamic sorption capicity (up to 1.3 meq/g). The anion exchangers with primary and secondary amino groups absorb sulfur dioxide at high relative humidity (more than 54 %) if their cation exchange capacity is several times less than the anion exchange capacity.
The sorption properties of new iminodiacetate fibrous cation exchanger FIBAN XC-1 synthesized on a chemically resistant matrix of polypropylene fiber with a grafted copolymer of styrene and divinylbenzene, which can withstand elevated temperatures and aggressive environments, were studied. It was shown that the fibrous chelate ion exchanger FIBAN XC-1 is an effective sorbent of heavy and non-ferrous metals from multi-ionic aqueous solutions under static and dynamic conditions. It was found that the cation exchanger operates at high speeds up to 20 column volumes / min in water purification from copper and lead ions (purification from Cu2+ – 82 % and purification from Pb2+– 65 %). It was found that the fibrous chelate ion exchanger FIBAN XC-1 is easily regenerated and does not lose its sorption and mechanical properties in the sorption– regeneration cycles.
The sorption properties of new iminodiacetate fibrous cation exchanger FIBAN XC-1 synthesized on a chemically resistant matrix of polypropylene fiber with a grafted copolymer of styrene and divinylbenzene, which can withstand elevated temperatures and aggressive environments, were studied. It was shown that the fibrous chelate ion exchanger FIBAN XC-1 is an effective sorbent of heavy and non-ferrous metals from multi-ionic aqueous solutions under static and dynamic conditions. It was found that the cation exchanger operates at high speeds up to 20 column volumes / min in water purification from copper and lead ions (purification from Cu 2+ – 82 % and purification from Pb 2+ – 65 %). It was found that the fibrous chelate ion exchanger FIBAN XC-1 is easily regenerated and does not lose its sorption and mechanical properties in the sorption– regeneration cycles.
Polymer analogous transformations of a "nitron" fiber were established and a new amino carboxylic fibrous cation exchanger FIBAN X-2 was obtained. It is shown that FIBAN X-2 is an effective sorbent of heavy and non-ferrous metals from multi-ionic aqueous solutions, regardless of the method of fiber amination. The cation exchanger obtained by amination of a "nitron" fiber in the vapor phase absorbs Mn+2 twice as much as the ion exchanger obtained by amination in the aqueous solution.
Мета роботи. У сучасних умовах іммобілізація лікарських засобів на полімерних носіях набуває все більшого значення, що пов’язане з вимогами до зменшення токсичності та пролонгації дії препаратів. Відома іммобілізація сульфаніламідних препаратів на стиромалі, метакрилатних полімерних матрицях, де фармакологічно активний сульфаніламід легко вивільняється з полімеру при застосуванні, в результаті кислотного гідролізу. Разом з тим спостерігається, що іммобілізовані сульфаніламіди, отримані на основі амінометильованого співполімеру стиролу з дивінілбензолом, незважаючи на стійкість до гідролізу, зберігають антибактеріальні властивості. З метою розширення прикладів ковалентної іммобілізації сульфаніламідів нами синтезовані 4-амінофенілсульфонаміди на гранульній і волокнистій формах співполімерів стиролу з дивінілбензолом через місткову групу SO2.Матеріали і методи. Як вихідну сировину використано макропористий гранульний співполімер стиролу з дивінілбензолом і сульфовані волокнисті форми прищепленого до поліпропіленової нитки співполімеру стиролу з дивінілбензолом. Сульфохлоруванням цих співполімерів отримано полімерні сульфохлориди, які використовували в реакції з 4-амінофенілсульфонамідом. Антибактеріальні властивості матеріалу досліджені за визначенням зон пригнічення росту тест-мікроорганізмів E.coli К-12 на поживному середовищі.Результати й обговорення. Будову синтезованих іммобілізованих 4-амінофенілсульфонамідів доведено методом ІЧ спектроскопії. Показано, що такі матеріали проявляють виражені антибактеріальні властивості щодо тест-культури мікроорганізмів E. coli К-12, незважаючи на їхню стійкість до гідролізу.Висновки. Зроблено припущення, що гідроліз матеріалів перебігає при специфічному ферментативному каталізі на поживному середовищі виділенням 4-амінофенілсульфонаміду.
The aim of the study. Today the immobilization of drugs to the polymeric carriers is increasingly important, due to the requirements to reduce the toxicity and prolongation of action of drugs. It is known the immobilization of the Sulfonamides on the Stiromali, methacrylate polymer matrices, wherein the pharmacologically active sulfanilamide easily remove from the polymer upon the application, by the acid hydrolysis. At the same time it is noted that immobilized sulfonamides derived from aminomethylated Styrene-divinylbenzene copolymer, although hydrolytic stability, maintain the antibacterial properties. In order to expand the examples of covalent immobilization of sulfonamides we synthesized 4-aminophenylsulfonamide on pellet and brous forms of styrene and divinylbenzene with SO2 as a bridging group. Materials and Methods. As a raw materials, we used the pellet macroporous sulfonated Styrene-divinylbenzene copolymer and copolymers Polypropylene and Styrene. Sulfochlorination of these copolymers the polymeric sulfonyl chlorides were obtained. This compounds were used in the reaction with 4-aminophenilsulfonamidom. Antibacterial properties of the material were studied by determining the growth inhibition zones of test E. coli K12 microorganism in a nutrient medium. Results and Discussion. The structure of synthesized immobilized 4-aminophenylsulfonamide proven by IR spectroscopy. It is shown that such materials exhibit a relatively pronounced antibacterial properties test culture of microorganisms E. coli K-12, in spite of their resistance to hydrolysis. Сonclusions. It is suggested that the hydrolysis of the materials takes place at a specic enzymatic catalysis in the medium with the release of 4-aminophenylsulfonamide.
Methods for synthesis and production of FIBAN ion exchange fibers, which are based on the radiation chemical and chemical modification of polypropylene and polyacrylonitrile fibers were developed. The possible applications of FIBAN materials for water and air purification from harmful impurities, separation of valuable products from the liquid media, and catalysis are considered.
Вивчена можливість застосування волокнистого поліамфоліту ФІБАН АК-22В як сорбенту для вилучення аніонних (кислотний червоний, прямий бордо) і катіонних (метиленовий блакитний, кристалічний фіолетовий) барвників із їх водних розчинів. Визначені оптимальні значення рН розчину і витрати поліамфоліту. Показано, що за допомогою поліамфоліту ФІБАН АК-22В можна вилучити (до 90—98 %) кислотний червоний, метиленовий блакитний, кристалічний фіолетовий і (до 56 %) прямий бордо.
The technology for producing a universal fibrous polyampholyte by single-step amination of nitron fiber with ethylenediamine or diethylenetriamine in the presence of alkali-metal carbonates was developed. The static exchange capacity of the polyampholyte basic groups was ~2.5 mg-eq/g; acidic groups, ~2.0 mg-eq/g. A pilot plant for producing ion exchanger with a throughput up to 4 ton/yr was put into operation. The fibrous polyampholyte in the carbonate form was used to purify air of acidic toxic gases. It was suitable after impregnation with mineral acids for ultrapurification from basic toxic gases over a broad range of relative humidity.
New N,S-containing fibrous ion exchangers were prepared by polymer-analogous transformations of Nitron fiber, involving amination with polyethylenepolyamines (ethylenediamine and diethylenetriamine), followed by the reaction of the aminated fiber with carbon disulfide. The materials obtained efficiently take up silver ions from multicomponent aqueous solutions of metal ions and from dilute solutions containing calcium ions.
By the condensation of substituted aldehydes of vanillin series with 1,3-propanediol in boiling benzene in the presence of sulfo cation exchanger FIBAN K-1 as catalyst functionally 2-R-substituted 1,3-dioxanes were synthesized.
The thermal transformations of anionites synthesized on the basis of a polyacrylonitrile fiber are studied. During the heat treatment of the weakly basic anionite FIBAN A-5, the cleavage of amino groups occurs via two routes. In the case of the strongly basic anionite FIBAN A-6, dealkylation and deamination occur during heating and the dealkylation of quaternary amino groups accompanied by formation of tertiary amino groups predominates. The thermal degradation of anionites proceeds much more intensely in an aqueous medium than in an atmosphere of inert gas owing to participation of water hydroxyl in the mentioned reactions.
Polymer-analogous transformations of a Nitron fiber were studied. These transformations include its amination with ethylenediamine, diethylenetriamine, and tetraethylenetriamine, followed by phosphorylation with PCl3 under the Kabachnik-Fields reaction conditions. Nitrogen- and phosphorus-containing ion exchangers were examined as sorbents of heavy and nonferrous metals from aqueous solutions, and zinc ions from dilute solutions on the background of calcium ions.
The possibility of modifying oxidized asphalt by performing polycondensation of maleic anhydride with aliphatic amines of various chemical structures in the dispersion medium was considered. The influence of the reactant structures and reaction conditions on the physicomechanical and structural-rheological properties of the polymer-modified asphalt was examined.