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ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
UDC541.64:512.678
SYNTHESIS OF PARA-AMINOPHENYL CYCLOPROPYLMETHACRYLATE AND ITS RADICAL COPOLYMERIZATION WITH STYRENE
V.A.Vahabova, A.F.Mammadova, K.Q.Guliyev
Institute of Polymer Materials, Ministry of Science and Education of the Republic ofAzerbaijan
vusalavahabova@gmail. com
Received 14.12.2022 Accepted 08.02.2023
The synthesis of a new monomer para-aminophenyl cyclopropyl methacrylate (APCM) was carried out, its radical copolymerization with styrene was investigated and some regularities of the process were studied. Its radical copolymerizations with styrene were carried out and the resulting copolymers were established in the structures. Based on the IR-NMR and UV spectra, it was found that the copolymeriza-tion process of para-aminophenyl cyclopropyl methacrylate proceeds through the double bond, and the substituents, para-aminophenyl cyclopropyl fragment, remain in the side macrochain. The values of the relative activity constants of monomer were determined and the parameters Q and e were calculated according to Alfrey and Pras. The copolymerization constants of the specified compound (r1) with styrene (r2) calculated by the Feinman-Ross method are r1=0.45, r2=0.22, the values of parameters Q and e: Q=0.024 and e=-2.316, respectively. It was revealed that the resulting copolymer has a sufficiently high biomedical activity, which opens the possibility of using this copolymer as a bactericide.
Keywords: para-aminophenylcyclopropyl methacrylate, biological activity, bactericide.
doi.org/10.32737/0005-2531-2023-2-131-137 Introduction
Polymers containing functionally active groups in their composition have a wide range of medical and biological activities and are used as bactericides, fungicides, and drugs. Most often, to obtain such polymers, monomers of the vinyl and new monomer series containing car-bonyls and amino groups in the structure are used. With this in mind, there is a great interest of researchers in obtaining new types of antimicrobial polymers for use in medicine [5-12].
Cyclopropane-containing compounds are known to be effective and relatively safe bio-cides with high biological activity [13-18]. Scientific research aimed at the development of new effective methods of obtaining polymers possessing a complex of predetermined properties retains its relevance.In this connection, it is interesting to study the reactions of radical co-polymerization of new binary systems, with specified complex properties, including particularly high biocidal activity of the synthesized copolymer.
Polymers containing cyclopropane units with different functional substituents in mac-romolecules are of great interest, as they are
characterized by a balanced complex of properties, including antimicrobial, photosensitivity, optical transparency, and can be used in medicine, as well as in microelectronics and optics.
The aim of this work is the synthesis of a new monomer of para-aminophenyl cyclo-propyl methacrylate, the investigation of its radical copolymerization with styrene, the study of some regularities of the copolymerization process and the analysis of their structure, as well as the evaluation of the reactivity and its bactericidal properties.
Experimental Part
Synthesis of paraaminophenylcyclopro-pyl methacrylate
0.5 mol (81.5 g) of 2-p-aminophenyl-1-p-hydroxymethylcyclopropane in tertiary amine medium was placed in a flask under reflux. Then 0.6 mol of methacryloyl chloride in 30 ml of absolute benzene was added dropwise for 2 hours at 300C with stirring. After completion of the reaction, the mixture was extracted with sulfuric ether, dried, distilled into light fractions and then into the main fraction under reduced pressure. Copolymerization of synthesized mo-
nomer with styrene was carried out in sealed ampoules in nitrogen atmosphere, in a solution of absolute benzene. The total concentration of the initial monomers was constant at 1.0 mol/l, and the ratio of the starting monomers varied in the ratios shown in the Table 1. The polymerization solution containing the monomer and the initiator (DAA-dinitrilazobisobutyric acid), interfered with glass ampoule, the mixture was blown by a flow of oxygen-free nitrogen for 5 minutes, the mixture was blown by a flow of oxygen-free nitrogen for 5 minutes, then the vial was tightly closed and placed in a thermostat at 343 K. The resulting copolymers of different composition of the comonomers were purified by double reprecipitation from a benzene solution in methanol, dried at reduced pressure (15-20 mm Hg) at 300C to constant mass.
The characteristic viscosity was determined in benzene in the Ubbelode viscometer. The characteristic viscosity was [q]=0.65 dl/g. The composition of the copolymer was determined by elemental analysis by nitrogen content, copolymer of aminophenylcyclopropyl methacrylate with styrene C22O2H25N. Found, %: C= 78.8; H=7.46; N=4.18. Calculated, %: C= 78.7; H=7.32; N=4.2.
Results and discussion
The copolymer of p-aminophenylcyc-lopropyl methacrylate with styrene was synthesized to study the dependence of biocidal properties of new cyclopropane-containing polymers
on the polymer chain composition. The copol-ymerization was carried out at a total concentration of comonomers of 1 mol/l under the action of dinitrileazoisobutyric acid, used as an initiator, 2*10-3 mol/l in benzene at 700C to a conversion of 8-10%. Table 1 shows the dependences of the content of comonomer units in the synthesized copolymers on the composition of the initial monomer mixture.
As follows from the obtained values of r1 and r2, aminophenylcyclopropylmethacrylateis a more active monomer than styrene.
The highest activity of the APCM monomer in radical copolymerization is also confirmed by UV spectra (Figure 1). The synthesized monomer exhibits UV-absorption bands at 280-290 nm due to (n-n) transitions. This fact makes it possible to state that this compound represents a conjugated system.
Apparently, spatial factors play an important role in the growth stage of the chain. Another important factor affecting the nature of polymerization may be the relative stability of the radical responsible for the chain growth. The copolymerization constants for this monomer pair were determined by the data of the element analysis on the nitrogen content, by the Feiman-Ross method [19], the parameters Q and e were calculated by Alfrey-Prais [20]. It was also found that in this case the copolymer is enriched with APCM units. All the data obtained are given in Table 1.
Composition of the initial mixture, mol% Nitrogen content N% Composition of copolymers, mol % Copolymerization constants Q-e Parameters
M1 M2 m1 m2 r: r2 ri- r2 Q1 e1
10 90 1.67 25.93 74.07
25 75 2.61 40.5 59.5
50 50 3.49 54.13 45.87 0.45 0.22 0.1 0.024 -2.316
75 25 4.43 68.66 31.34
90 10 5.36 83.14 16.86
Table 1. Dependences of the content of comonomer units in the synthesized copolymers on the composition of the initial monomer mixture
Fig. 1. UV spectracopolymer para-aminophenyl cyclopropyl methacrylate with styrene
Spectral (IR and NMR) and elemental analyses of the sample were carried out in order to reveal the structure of the synthesized copol-ymer. By comparing the IR spectra of the obtained copolymer with the spectra of the original monomers, which belong to the 1720 cm-1 absorption bands, the absorption bands characterizing the valence vibrations of the carbonyl group in the formed polymers at 1730 cm-1 were found. The shift of the maximum of the absorption band characterizing the >C=O group is probably related to the opening of the double bond, which leads to a violation of the conjugation and redistribution of the electron density in the system.
Vibrations of the benzene ring belong to the absorption bands at 1608 cm-1, 1580 cm-1, 1496 cm-1 and 1456 cm-1 in the spectra of polymers and are present in all samples of the co-polymer. The absorption bands in the region of 1035-1040 cm-1 can be attributed to cyclopropane groups observed in the IR spectra (Figure 2) of both the initial APCM monomer and the synthesized copolymer. Changes in the IR spectra of the copolymer, namely, the absence of absorption bands in the areas of 900-1000 cm-1, 1635-1640 cm-1, refers to the deformation and valence vibrations of the double bond of the vinyl group. In the NMR spectrum (Figure 3) of the copolymer, resonant signals characteristic of the protons of the benzene nucleus (5=6.80-7.60 m.d) and the cyclopropane ring (5=0.25-2.65 m.d) are clearly present, and proton signals
related to protons of the vinyl group (5=4.50-5.05 m.d) are absent in a polymer sample.
The results of the spectral analysis showed that copolymerization occurs only at the double bond of the vinyl group, and the reactive fragments in the side macrochain remain unchanged.
— OCH2—CH-CH— CH2
-NH,
The structures of the produced copoly-mers are presented below.
CH2—ÇH
o = c— x
? О
x=
-о—CH2—CH —CH—^ NH2 CH2
It was found that the synthesized copol-ymer exhibits high bactericidal activity, which is associated not only with the content of APDC in the copolymer, but also with the nature of the distribution of its links in the chain.
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 €00
Wavenumber
Fig. 2. IR spectracopolymer para-aminophenylcyclopropyl methacrylate with styrene.
Fig. 3. NMR spectracopolymer para-aminophenylcyclopropyl methacrylate with styrene
The antimicrobial properties of the synthesized substance were studied by a known method - serial dilutions. For this purpose, a 1% solution of the new substance in dioxane was diluted in sterile distilled water in the following ratios (1:100, 1:200, 1:400, 1:800), (1, 2, 3, 4). The effect of the synthesized copolymer was studied in comparison with ethanol and di-oxane. Gram-positive microorganisms, Staphylococcus aureus (St. aureus), gram-negative intestinal spores (E.coli), pigment-forming blue-green purulent spores (Ps.aeruginosa) and fungi of the genus Candida, which were taken from C.albicans, were used as a test culture. MPA (meaty peptone agar) was used to grow bacteria, and Sabouraud nutrient medium was used to grow fungi. Sowings were carried out every 10, 20, 40, 60 minutes, incubated for 24 hours in a thermostat at 370C for bacteria and 48 hours in a thermostat at 280C for fungi. In the experiments, 1 -2 drops of an emulsion containing 500 million microbial particles per 1 ml were instilled into each tube (for each dilution). Sowing was carried out from each tube every 10-20 minutes for 1 hour. The antimicrobial effects of the newly synthesized polymer and the control substances are shown in the table. As can be seen from the table, the studied sub-
stances had different effects on different types of microorganisms. In general, all synthesized substances have an antimicrobial effect.
The antimicrobial activity of the synthesized polymer has been investigated and it has been shown that the compound affects various types of microorganisms in different ways. In general, allinvestigated substances have antimicrobial activity. The copolymer itself has an active antimicrobial activity in dioxane solution. These substances showed more active antimicrobial properties against Gram-positive microbes and Candida. For example: a copoly-mer of aminophenilcyclopropyl methacrylate with styrene in a ratio of 1:400 and the copoly-mer preparations destroyed St. aureus within 20 minutes (was finished). All substances killed Candida fungus in a ratio of 1:400 for 10 minutes, and the preparation of polymethyl-methacrylate in a ratio of 1:800 - for 20 minutes. The copolymer aminophenylcyc-lopropyl methacrylate and styrene killed Candida, as well as staphylococci and green pus in a ratio of 1:800 - within 1 hour. As a result, it has been determined that the tested copolymer based on aminophenylcyclopropyl methacrylate can be used both as a bactericidal and fungicid-al agent.
Table 2. Antimicrobial actions of aminophenyl cyclopropyl methacrylate (p-APCPM) copolymers and styrene
Test cultures Exposition duration (min.) Investigated Substances Control Substances
copolymer polystyrene dioxane ethanol
1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
St.aureus 10 - - + + - - - + - - + + - + + +
20 - - + + - - - + - - + + - + + +
40 - - - + - - - - - - - + - + + +
60 + + +
Ps.aeruginoza 10 - - - + - - - + - - - + + + + +
20 - - - + - - - + - - - + - + + +
40 - - - + - - - + - - - + - + + +
60 - - - + - - - + - - - + - + + +
E. coli 10 - - + + - - - + - - - + + + + +
20 - - - + - - - + - - - + - + + +
40 - - - + - - - + - - - + - + + +
60 + - + + +
Candida albicans 10 - - + + - - - + - - - + + + + +
20 - - - + - - - - - - - + + + + +
40 - - - + - - - - - - - + - + + +
60 + - + + +
Table 2 shows that the copolymer obtained has high antimicrobial properties. It has been shown that antimicrobial properties of this copolymer are mainly due to the presence of the p-APCP fragment in the macrochain.
As a result, it has been found that the synthesized copolymer can be used in medicine.
Conclusions
1. A new polyfunctional monomer, a para-aminophenylcyclopropyl methacrylate, has been synthesized. Its radical copolymerizations with styrene were carried out and the obtained co-polymers were found in the structure. Based on IR-NMR, it has been determined that the process of copolymerization of para-aminophe-nylcyclopropyl methacrylate proceeds through the double bond and the substituents remain in the side macrochain.
2. Based on the data of the constant "r1, r2", it is shown that the copolymerization of this pa-ra-aminophenylcyclopropyl methacrylate, is more active than styrene.
3. The biological tests showed that the synthesized polymer exhibits high antimicrobial properties. It was found that these properties depend on the composition of the copolymer, since with the entrainment of para-aminophenyl cyclopropyl methacrylate, the antimicrobial properties increase.
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AMiNOFENiL PARA-TSiKLOPROPiLMETAKRiLATIN SiNTEZi УЭ ONUN STiROLLA RADiKAL
SOPOLiMERLO^MOSi
V.O.Vahabova, A.F.Mammadova, K.Q.Quliyev
Yeni para-aminofeniltsiklopropilmetakrilat (AFTM) monomeri sintez edilmi§, onun stirolla radikalsopolimerla§masi tadqiqedilmi? va prosesin bazi qanunauygunluqlari öyranilmiijdir. Onunstirolla radikal sopolimerla§masi apanlmi§ va alinan sopolimerlarin qurulu§lari tarkibinda müayyan edilmi§dir. IR, NMR, elaca da UV spektrlari asasinda müayyan edilmi§dir ki, para-aminofenilsiklopropilmetakrilatin sopolimerla§masi prosesi ikiqat rabita vasitasi ila gedir va avazedicilar - para-aminofenilsiklopropilmetakrilat yan makrozancirda qalir. Monomerlarin nisbi aktivlik sabitlarinin qiymatlari tayin olunmu? va Q va e parametrlari Alfrey va Praysa uygun olaraq hesablanmi§dir. Göstarilan birla§manin (r1) stirol (r2) ila sopolimerla§ma sabitlari Feynman-Ross üsulu ila hesablanmi? r1=0.45, r2=0.22, Q va e parametrlarinin qiymatlari: Q=0,023 va e=1.92. Müayyan edilmi§dir ki, alinan sopolimer kifayat qadar yüksak tibbi-bioloji faalliga malikdir va bu da hamin sopolimerdan bakterisid kimi istifada etmak imkanini yaradir.
Agar sözlar: para-aminofeniltsiklopropilmetakrilat, bioloji aktivlik, bakterisid.
СИНТЕЗ ПАРА АМИНОФЕНИЛ ЦИКЛОПРОПИЛМЕТАКРИЛАТА И ЕГО РАДИКАЛЬНАЯ
СОПОЛИМЕРИЗАЦИИ СО СТИРОЛОМ
В.Е.Ваxабова, А.Ф.Маммадова,К.Г.Кулиев
Проведен синтез нового мономера пара-аминофенил циклопропилметакрилата (АФЦМ), исследована его радикальная сополимеризация со стиролом и изучены некоторые закономерности процесса. Осуществлены его радикальные сополимеризации со стиролом, установленные в составе структур полученные сополимеры. На основании ИК-, ЯМР, а также УФ-спектрами установлено, что процесс сополимеризации пара-аминофенил-циклопропилметакрилата протекает по двойной связи, а заместители - пара-аминофенилциклопропил-метакрилат остаются в боковой макроцепи. Определены значения констант отшсительной активности мономеров и рассчитаны параметры Q и e по Алфрею и Прасу. Константы сополимеризации указанного соединения (rj) со стиролом (r2), рассчитанные по методу Файнмана-Росса составляют rj=0.45, r2=0.22, значения параметров Q и e: Q=0.023 и e=1.92 соответственно. Выявлено, что полученный сополимер обладает достаточно высокой медико-биологической активностью, что открывает возможность использования данного сополимера в качестве бактерицида.
Ключевые слова: пара-аминофенилциклопропилметакрилат, биологическая активность, бактерицид.
