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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 4 2021 ISSN 0005-2531 (Print)
UDC 547.11:615.212.4
PREPARATION AND STUDY OF THE PROPERTIES OF THE COPOLYMER OF CYCLIC UNSATURATED BISMALEIMIDE WITH STYRENE
A.I.Alikhanova, R.Sh.Rasulzade
Institute of Polymer Materials, NAS of Azerbaijan
aygun81@mail.ru
Received 21.06.2021 Accepted 12.08.2021
The paper is devoted to the study of regularities of radicai copolymerization reactions of unsaturated cyclic N,N'-bisimides (M1) with styrene (M2), the study of dependence of copolymerization reaction rate, composition of obtained copolymers, composition and estimated molecular weight on the composition of the initial monomer mixture. With the increase of bismakimide amount in the initial monomer mixture a decrease of copolymerization reaction yield and molecular weight of the obtained copolymers was observed. This fact can be explained by active participation of bismaleimide in chain transfer in radical copolymeri-zation reaction. The composition of the obtained copolymers in all cases is rich in styrene links. Keywords: unsaturated cyclic bisimides, styrene, copolymer, copolymerization constants, antimicrobial and fungicidal properties.
doi.org/10.32737/0005-2531-2021-4-25-29
Introduction
Polystyrene (PS) is of great importance as a modern construction material in combination with general-purpose styrofoam, impact-resistant polystyrene and ABC (acrylonitrile-butadiene-styrene). Although polystyrene makes up 6% of the world's polymer materials in the form of plastic mass, it is widely used in many areas of household chemicals, construction and automotive industries [1, 2].
One of the most widely used areas of PS is the production of packaging material for food products by thermoforming. It is important that the resulting polystyrene of this type is resistant to widespread microbes and microfungi [3, 4].
One of the most common methods for the formation of antibacterial properties of polymers is the inclusion of a monomer fragment with antibacterial properties into macrochains at the stage of their synthesis [5].
The aim of this work is to develop a technology for the synthesis of styrene copolymers with unsaturated cyclic N,N'-bisimide of maleic acid to obtain an antibacterial copolymer and to study its physico-mechanical and bactericidal properties [6].
Experimental part
N,N'-(4,4-diphenylmethane)bismaleinimide obtained by a known method by the interaction of (4,4-diphenylmethane)diamine with maleic
anhydride [7].
Styrene (C6H5-CH=CH2) - used industrial (b.p. - 25.50C, p - 0.9060, - 1.5462).
The copolymerization of N,N'-(4,4-diphe-nylmethane)bisimide of maleic acid (M1) with styrene (M2) was carried out in a glass ampoule in a solution of methyl ethyl ketone in the presence of 0.2% benzene peroxide (BP) at a temperature of 750C for 4 hours. The total density of the resulting mixture of monomers was constant, 1.0 mol/l, and the ratio of monomers changes accordingly. The resulting copolymer was precipitated methanol from methyl ethyl ketone several times, and then dried in a vacuum (30-40 mm Hg) at a temperature of 400C to a constant weight.
The obtained copolymer in the form of a white powder is highly soluble in methyl ethyl ketone and chlorinated organic solvents. The composition of copolymers is determined by the value of the unit of etherization.
The characteristic viscosity was determined by a Ubbelode viscometer [8]. The IR spectra of the samples were recorded on an Alpha-IR Fourier spectrometer (BRUKER, Germany), in the range of 600-4000 cm-1 [9].
Results and discussion
The copolymerization reaction was carried out as follows:
PH=CH.
The parameters of copolymerization (relative activity of monomers - r1 and r2) were determined kinetically. There is also a dependence on composition, composition and properties. Constants of copolymerization were calculated according to the Mayo-Lewis equation.
The composition and structure of the co-polymers were determined based on the IR spectra of the resulting styrene copolymer (Figure 1a) and styrene copolymer (Figure 1b). Comparison of the IR spectra (Figures 1a and 1b) showed that in the spectra of the styrene copolymer, absorption bands were observed in the region of 1773 cm-1 and there were no absorption bands up to the (C-O) group, (N-C), while in the IR spectra of the resulting copo-lymer with bismaleinimide, absorption bands of the (C=O) bond were found at 1694 cm-1, for
(C-C) bonds in the region of 1707 cm1, for (N-C) bonds in the region of 1326 cm-1.
The parameters of the copolymer microstructure were calculated based on the copoly-merization constants (Table 1).
From Table 1, it can be seen that the composition of the copolymers is enriched in styrene units. With an increase in the number of bismaleinimide units in the copolymer of bis-maleinimide with St, the rate and degree of the polymerization reaction decreases. (r1 = 0.01 for a pair of bismaleinimide-St; r2 = 12.5).
As can be seen from Table 2, with an increase in the relative amount of bismaleinimide in the monomer mixture, a sharp decrease in the yield of the copolymer, the characteristic viscosity and the average molecular weight of the copolymer is observed.
Fig. 1a. IR spectrum of N, N'- (4.4-diphenylmethane)bismaleinimide -Styrene copolymers.
PREPARATION AND STUDY OF THE PROPERTIES.
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Fig. 1b. IR spectrum of polystyrene.
Table 1. Indicators for calculating the relative activity of monomers in the copolymerization reactions of N, N'-(4,4-diphenylmethane)bismaleinimide (Mt) and Styrene (M2)
Initial mixture of monomers Yield, % The amount of monomer in the copolymer is % r1 r2 rrr2 Microstructure of copolymers
Mj M2 m: m2 LM, Lm2 R
10 90 16.0 0.06 99.4 0.12 12.51 0.10 1.002 164.8 1.204
25 75 19.0 1.7 98.3 1.006 55.6 3.53
50 50 15.5 5 95 1.02 19.2 9.89
75 25 16.5 13 87 1.06 7.06 24.63
90 10 12.5 28 72 1.18 3.02 47.61
Lm1 and Lm2-the ratio of monomer blocks; R-the Harvurd block coefficient.
Table 2. Effect of their composition on the properties of copolymers obtained in the copolymerization reactions of N,
N'- (4,4-diphenylmethane)bismaleinimide (M^ and styrene (M2)
№ The amount of styrene in the monomer mixture, mass % Amount of m1 in copolymers, mass % Yield, % M dl/g. Viscosity, T0C
1 0.0 0 84.0 0.78 83
2 5.0 0.32 20.5 0.66 77
3 10.0 1.20 15.2 0.43 72
4 25.0 2.5 12.00 0.30 70
5 50.0 4.0 10.5 0.22 66
The research of antimiocrobe properties of the copolymer was studied in series by dilution method [10-12]. It was held in the following ratios (1:100, 1:200, 1:400, 1:800). Newly synthesized copolymer influence to various microorganisms differently and when diluted in 1:100 ratio substance show strong antimicrobial activity against all tested test cultures.
Antimicrobe impact of copolymer was stu-
died comparatively with alcohol, rivanol and nitrofungine that are widely used in medicine. The tests are repeated every 15, 30, 45, 60 minutes. The duration of incubation for bacteria is 18-24 hours at 370C.
Tested substance has killed Candida in 1:800 ratio dilution during 10 minute. Examined copolymer can be suggested as antimicrobial substance.
Conclusions
1. The regularities of the radical copolymerization reactions of unsaturated cyclic N,N'-bisimides of maleic acid with styrene were studied, the composition and structure of the obtained copolymers were also studied on the basis of IR spectra.
2. The dependences of copolymerization reaction rate, composition of the obtained copo-lymers, composition and molecular weight estimation on the composition of the initial monomer mixture were studied. With increasing the amount of bismaleimide in the initial monomer mixture there is a decrease in the yield of copolyme-rization reaction and the molecular weight of the obtained copolymers. This fact can be explained by active participation of bismaleimide in chain transfer in radical copolymerization reaction.
3. It has been shown that in the copolymerization reaction of maleic acid bisimide with styrene, styrene has a high activity. As the number of bismaleinimide links in the copolymer of bis-maleinimide with St decreases, the rate and degree of polymerization reaction decreases.
The antimicrobial properties of the copo-lymer were studied in series by dilution method. The obtained copolymer has antimicrobial properties against Candida fungus. The studied compound can be proposed as an antimicrobial agent.
References
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6. AlikhanovaA.I., Rasulzade N.Sh. Polucheniye i issledovaniye sopolimerov tsiklicheskikh bisimi-dov so stirolom. IV Vseross. Konf. "Khimiya i khimicheskaya tekhnologiya: dostizheniya i perspektivy", Kuzbasskiy gos. tekhn. Un-tet imeni T.F.Gorbacheva, Rossiya, 2020. C. 671-672.
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8. Rafikov S.R., Pavlova S.A., Tverdokhlebova I.I. Metody opredeleniya molekulyarnykh vesov i polidispersnosti vysokomolekulyarnykh soyedine-niy. M.: Izd. AN SSSR., 1963. 334 s.
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TSIKLIK DOYMAMIS BISMALEIMIDIN STIROLLA BIRGOPOLIMERININ ALINMASI VO
XASSOLORiNiN TODQiQi
A.I.Olixanova, Rg.Rasulzada
Maqala doymamiç tsiklik imidlarin (М1) stirol (М2) ils radikal birgapolimerlaçma reaksiyalannin tadqiqinin naticalari va qanunauygunluqlarinin öyranilmasina hasr olunmuçdur. Birgapolimerlaçma reaksiyasinin sürati, alinan birgapolimerlarin tarkibi va molekul kütlasinin qiymatinin ilkin monomer qançiginin tarkibindan asililigi ôyranilmiçdir. ilkin monomer qançiginin tarkibinda bismaleimidin miqdannin artmasi ila birgapolimerlaçma reaksiyasinin çiximinin va alinan birgapolimerlarin molekul kütlasinin azalmasi mûçahida edilir. Bu fakti radikal birgapolimerlaçma reaksiyasinda bisimid zancirin ötürülmasi reaksiyasinda aktiv içtirak etmasila izah etmak olar. Alinan birgapolimerlarin tarkibi bütün hallarda stirol manqalan ila zangin olur.
Açar sözlar: doymamiç tsiklik imidhr, stirol, birgapolimer, sopolimer, birgapolimerhçma sabitbri, antibakterial va funqal xassalar.
PREPARATION AND STUDY OF THE PROPERTIES
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ПОЛУЧЕНИЕ И ИЗУЧЕНИЕ СВОЙСТВ СОПОЛИМЕРА ЦИКЛИЧЕСКОГО НЕНАСЫЩЕННОГО
БИСМАЛЕИМИДА СО СТИРОЛОМ
А.И.Алиханова, Р.Ш.Расулзаде
Статья посвящена изучению закономерностей получения реакций радикальной сополимеризации ненасыщенных циклических М,№-бисимидов (М1) со стиролом (М2), изучению зависимости скорости реакции сополимеризации, состава полученных сополимеров, состава и оценки молекулярной массы от состава исходной мономерной смеси. С увеличением количества бисмалеимида в исходной мономерной смеси наблюдается снижение выхода реакции сополимеризации и молекулярной массы полученных сополимеров. Этот факт можно объяснить активным участием бисимида в передаче цепи в реакции радикальной сополимеризации. Состав полученных сополимеров во всех случаях богат стирольными звеньями.
Ключевые слова: ненасыщенные циклические бисимиды, стирол, сополимер, константы сополимеризации, антибактериальные и фунгицидные свойства.
