scholarly journals POLYMERIZATION BY INTERACTION a-HALOACRYLIC ACIDS WITH TERTIARY AMINES

Author(s):  
Юсуф Ахматович Малкандуев ◽  
Анета Ахмедовна Кокоева ◽  
Абдулахат Турапович Джалилов

Приведены результаты самопроизвольной полимеризации а -хлоракриловой и а -бромакриловой кислот с третичными аминами при невысокой температуре. В результате самопроизвольной полимеризации при взаимодействии а -галоидакриловых кислот с третичными аминами образуются полимеры, содержащие четвертичные аммониевые группы. С целью подтверждения данного предположения были проведены ЯМР- и ИК-спектроскопические исследования продуктов самопроизвольной полимеризации. Показано, что сопутствующая реакция кватернизации, спонтанной полимеризации, имеет место как в смеси реагентов, так и в присутствии растворителя, т.е. и при смешении непредельного амина и галоидного алкила. Изучены кинетические закономерности реакции полимеризации и показано, что реакция кватернизации, являющаяся лимитирующей стадией процесса самопроизвольной полимеризации, протекает по S 2 - механизму. Описываются первые попытки получения новых нанокомпозиционных материалов на основе синтезированных сополимеров и модифицированного монтмориллонита. Анализ литературных данных показывает, что особенности получения нанокомпозитов на основе Na - монтмориллонита и водорастворимых сополимеров ранее не изучались. The results of spontaneous polymerization of а -chloroacrylic and а -bromoacrylic acids with tertiary amines at a low temperature are presented. As a result of spontaneous polymerization during the interaction of а -halodacrylic acids with tertiary amines, polymers containing quaternary ammonium groups are formed. In order to confirm this assumption, nuclear magnetic resonance and infrared spectroscopic studies of the products of the spontaneous polymerization were carried out. Spontaneous polymerization proceeds, consisting of two stages: the quaternization reaction and the polymerization reaction. The kinetic regularities of the polymerization reaction were studied and it was shown that the quaternization reaction, which is the limiting stage of the spontaneous polymerization process, proceeds according to the S 2 - mechanism. It has described the first attempts to obtain new nanocomposite materials based on synthesized copolymers and modified montmorillonite. Analysis of the literature data shows that the features of the preparation of nanocomposites based on Na - montmorillonite and water-soluble copolymers have not been previously studied.

2021 ◽  
Vol 899 ◽  
pp. 262-268
Author(s):  
Yusuf A. Malkanduev ◽  
Aneta A. Kokoeva ◽  
Аblulakhat T. Dzhalilov

The reaction of spontaneous polymerization in the system of N, N-diethylaminoethyl methacrylate with allyl chloride and bromide, orthophosphoric acid in ethanol and dimethyl sulfoxide solutions is considered. Spontaneous polymerization proceeds, consisting of two stages: the quaternization reaction and the polymerization reaction. It was shown that the accompanying reaction of quaternization, spontaneous polymerization, takes place both in a mixture of reagents and in the presence of a solvent, in other words, and by mixing an unsaturated amine and an alkyl halide.


2021 ◽  
Vol 36 (1) ◽  
pp. 356-361
Author(s):  
A.I. Sharipova ◽  
I.L. Akhmadjоnov ◽  
A.B. Аbdikamalova ◽  
Kh.I. Akbarov ◽  
Sh.A. Kuldasheva

The issues of the synthesis of a water-soluble polymer preparation, which can find application in agriculture as a structure-forming agent of soils and mobile sands to prevent water, wind, mechanical erosion, increase fertility, moisture absorption, moisture retention, consolidation of soils, dumps, and mobile sands to eliminate negative effects on the environment. Maleic acid and acrylamide were chosen as monomers for the copolymerization reaction, and potassium persulfate was chosen as the initiator. As it turned out, an increase in the concentration of the initiator from 0.01 to 0.05% (by weight of monomers) promotes an increase in the rate of the polymerization process, maintaining its value for a longer time, reducing the time of this process from 7.0-6.5 to 5, 5-6 hours. In this case, the yield of the polymerization reaction increased exactly from 81.2 to 96.0% for the reaction with the ratio of starting materials 1: 5. When a small amount of alkali is introduced into the reaction mixture, high molecular weight polymers can be obtained. In this case, the yield of the process increases, and the reaction time is reduced by 2-3 hours. Analysis of the kinetics of fixing processes using synthesized and various other reagents, as well as changes in the plastic strength of sands, showed the dependence of the conditions of penetration of the fixer with the formation of a free flow in space under the influence of gravitational or capillary forces on the type of binding agent and on the composition of the sand itself.


Author(s):  
Юсуф Ахматович Малкандуев ◽  
Мадина Биляловна Бегиева ◽  
Анета Ахмедовна Кокоева ◽  
Абдулах Касбулатович Микитаев ◽  
Абдулахат Турапович Джалилов

Приведены результаты сополимеризации а - галогенов акриловой кислоты с N - винилпирролидоном в присутствии аминирующих агентов, при низких температурах в органической среде. ИК-спектры полученных сополимеров подтверждают реакцию аминирования. Исследованы зависимости приведенной вязкости водных растворов синтезированных полимеров и наблюдается «полиэлектролитное набухание». Синтезированные аминированные полимеры образовывают внутрикомплексные соединения с галогенидами двухвалентных металлов при комнатной температуре. В работе описываются первые попытки получения новых нанокомпозиционных материалов на основе синтезированных сополимеров и модифицированного монтмориллонита. Анализ литературных данных показывает, что особенности получения нанокомпозитов на основе Na - монтмориллонита и водорастворимых сополимеров ранее не изучались. The paper presents results on copolymerization of a-halogens acrylic acid and N - vinylpyrrolidone in the presence of aminating agents at low temperatures in an organic environment. The IR spectra of the obtained copolymers confirm the amination reaction. The dependences of the reduced viscosity of synthesized polymers aqueous solutions were studied and a «polyelectrolyte swelling» was observed. The synthesized aminated polymers form internal complex compounds with divalent metal halides at room temperature. This paper describes the first attempts to obtain new nanocomposite materials based on synthesized copolymers and modified montmorillonite. Analysis of the literature data shows that the features of obtaining nanocomposites based on Na -montmorillonite and water-soluble copolymers have not been studied before.


Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1640
Author(s):  
Massimiliano Lanzi ◽  
Debora Quadretti ◽  
Martina Marinelli ◽  
Yasamin Ziai ◽  
Elisabetta Salatelli ◽  
...  

A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.


2021 ◽  
pp. 096739112110245
Author(s):  
Amrita Sharma ◽  
PP Pande

It has been observed that acrylate monomers are very difficult to polymerize with the low cost nitroxide catalyst 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO). Therefore, costly acyclic nitroxides such as N-tert-butyl-N-(1-diethylphosphono-2,2-dimethyl)-N-oxyl, (SG1), 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) and TIPNO derivatives have to be used for the polymerization of the acrylic acid derivatives. There are very few reports on the use of TEMPO-derivatives toward the polymerization of n-butyl acrylate. Generally different reducing agents viz. glucose, ascorbic acid, hydroxyacetone etc. have been used to destroy excess TEMPO during the polymerization reaction. The acrylate polymerizations fail in the presence of TEMPO due to the strong C–O bond formed between the acrylate chain end and nitroxide. To the best of our knowledge, no literature report is available on the use of TEMPO without reducing agent or high temperature initiators, toward the polymerization of n-butyl acrylate. The present study has been carried out with a view to re-examine the application of low cost nitroxide TEMPO, so that it can be utilized towards the polymerization of acrylate monomers (e.g. n-butyl acrylate). We have been able to polymerize n-butyl acrylate using the nitroxide TEMPO as initiator (via a macroinitiator). In this synthesis, a polystyrene macroinitiator was synthesized in the first step from TEMPO, after this TEMPO end-capped styrene macroinitiator (PSt-TEMPO) is used to polymerize n-butyl acrylate monomer. The amount of macroinitiator taken was varied from 0.05% to 50% by weight of n-butyl acrylate monomer. The polymerization was carried out at 120°C by bulk polymerization method. The experimental findings showed a gradual increase in molecular weight of the polymer formed and decrease in the polydispersity index (PDI) with increase in amount of PSt-TEMPO macroinitiator taken. In all experiments conversion was more than 80%. These results indicate that the polymerization takes place through controlled polymerization process. Effect of different solvents on polymerization has also been investigated. In the following experiments TEMPO capped styrene has been used as macroinitiator leading to the successful synthesis of poly n-Butyl acrylate. It has been found that styrene macroinitiator is highly efficient for the nitroxide mediated polymerization, even in very small concentration for the synthesis of poly n-butyl acrylate. High concentration of macroinitiator results in the formation of block copolymers of polystyrene and poly ( n-butyl acrylate) viz. polystyrene-block-poly-( n-butyl acrylate). The use of TEMPO toward controlled polymerization is of much importance, because it is the nitroxide commercially available at the lowest cost.


2018 ◽  
Vol 935 ◽  
pp. 134-139 ◽  
Author(s):  
Timur A. Borukaev ◽  
A.Kh. Malamatov ◽  
M.K. Vindizheva ◽  
A.V. Orlov ◽  
S.G. Kiseleva

Oxidative polymerization of 3-amino,2'-,(3')-nitrodiphenylazomethine was carried out in various ways. A possible mechanism for the polymerization of 3-amino,2'-,(3')- nitrodiphenylazomethine, where chain growth occurs as type N-C, is shown. It has been found that the yield of the polymer product is affected by the polymerization process and time. The chemical structure of the polymers obtained is established. The study of the thermal properties of polymers showed a low thermal stability and the process of destruction proceeds in two stages.


2018 ◽  
Vol 73 (1) ◽  
pp. 59-68 ◽  
Author(s):  
A. G. Samokhin ◽  
Ju. N. Kozlova ◽  
D. V. Korneev ◽  
O. S. Taranov ◽  
E. A. Fedorov ◽  
...  

Background: The problem of bacterial colonization of implants used in medical practice continues to be relevant regardless of the material of the implant. Particular attention deserves polymeric implants, which are prepared ex tempore from polymethyl methacrylate, for example - duting orthopedic surgical interventions (so-called "bone cement"). The protection of such implants by antibiotic impregnation is subjected to multiple criticisms, therefore, as an alternative to antibiotics, lytic bacteriophages with a number of unique advantages can be used - however, no experimental studies have been published on the possibility of impregnating bacteriophages into polymethyl methacrylate and their antibacterial activity assessment under such conditions.Aims: to evaluate the possibility of physical placement of bacteriophages in polymethylmethacrylate and to characterize the lytic antibacterial effect of two different strains of bacteriophages when impregnated into polymer carrier ex tempore during the polymerization process in in vitro model.Materials and methods:  First stage - Atomic force microscopy (AFM) of polymethyl methacrylate samples for medical purposes was used to determine the presence and size of caverns in polymethyl methacrylate after completion of its polymerization at various reaction  temperatures (+6…+25°C and +18…+50°C).The second stage was performed in vitro and included an impregnation of two different bacteriophage strains (phage ph20 active against S. aureus and ph57 active against Ps. aeruginosa) into polymethyl methacrylate during the polymerization process, followed by determination of their antibacterial activity.Results: ACM showed the possibility of bacteriophages placement in the cavities of polymethyl methacrylate - the median of the section and the depth of cavities on the outer surface of the polymer sample polymerized at +18…+50°C were 100.0 and 40.0 nm, respectively, and on the surface of the transverse cleavage of the sample - 120.0 and 100.0 nm, respectively, which statistically did not differ from the geometric dimensions of the caverns of the sample polymerized at a temperature of +6…+25°C.The study of antibacterial activity showed that the ph20 bacteriophage impregnated in polymethyl methacrylate at +6…+25°C lost its effective titer within the first six days after the start of the experiment, while the phage ph57 retained an effective titer for at least 13 days.Conclusion: the study confirmed the possibility of bacteriophages impregnation into medical grade polymethyl methacrylate, maintaining the effective titer of the bacteriophage during phage emission into the external environment, which opens the way for the possible application of this method of bacteriophage delivery in clinical practice. It is also assumed that certain bacteriophages are susceptible to aggressive influences from the chemical components of "bone cement" and / or polymerization reaction products, which requires strict selection of bacteriophage strains that could be suitable for this method of delivery.


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