AZƏRBAYCAN KİMYA JURNALI № 3 2017 17

UDC 678.744.342:547.9
THE RESEARCH OF ANTIBACTERIAL PROPERTIES OF METHYL
METHACRYLATE AND METHACRYLOYL SALICYLATE COPOLYMERS
N.Sh.Rasulzadeh, A.H.Azizov , E.A.Ibadov, S.G.Zaynalova, N.Sh.Rasulov
The Institute of Polymer Materials, NAS of Azerbaijan
The Medical University of Azerbaijan
prof.niyazi@mail.ru
Received 19.05.2016
Copolymers of methyl methacrylate and methacryloyl salicylate in various proportions were synthesized
and their antibacterial properties studied. Minimal inhibitor concentration (MIC) of copolymers and
physiological solutions of sodium salt against St.aureus, Ps.aeruginoza, C.albicans, E.coli bacterias
were defined. It was determined that, antibacterial properties of copolymers keeping 5–10 mas.% meth-
acryloyl salicylate elementar unit are 2–4 times more in comparison with the polymethyl methacrylate.
Keywords: copolymer, methacryloyl salicylate, antibacterial, properties.

Introduction Experimental part

One of the rapidly growing directions of
high molecular compounds is a preparation of
new polymer materials’ obtaining technology
that can be used in medicine.
The most of medical-biological purpose
polymers are obtained by polymerization and
copolymerization methods. The inclusion of
elementary members with biological active
group to macromolecular chain at synthesis
stage creates high biological properties in them.
Among medical-biological purpose polymers
N-vinyl pyrrolidon, N-vinyl carbozole base
polymers are widely researched and they have
definite application areas [1].
Recent years the numerous salicylic acid
and its derivatives are very significant from the
point of view of obtaining vinyl of content mon-
omers from them and conversion into different
polymer materials. Research works have been car-
ried out on obtaining of allyl-, vinyl-, methacryl
derivatives of salicylic acid and studying copoly-
merization reactions with methacrylate [2, 3].
The aim of the presented work is the
synthesis of copolymers of different content on
the base of methacryloyl salicylate and methyl
methacrylate keeping biological active salicylic
group and study their antibacterial properties.
Obtaining polymethyl methacrylates with
antibacterial property and using them in the
preparation of tooth prostheses also attract in-
terest practically.
Salicylic ether of methacryl acid is syn-
thesized via known method [3].
In order to obtain methyl methacrylate
(MMA) copolymers with methacryloyl salicy-
late (MST) 9.0 g MMA, 1.0 g MST, 0.02 g ben-
zoyl peroxide (BP) and 20 ml dioxane contain-
ing reaction mixture are poured into 50 ml glass
ampoule. The ampoule is cooled, its air is ex-
pelled with the flow of nitrogen, then it is
closed with welding and is placed in thermostat,
heated at 650C temperature for 8 hours. Ob-
tained solid polymer solution is precipitated in
ethanol, is washed with ether and is dried in
vacuum drying at 400C till getting constant
weight. The yield is 7.5 g (75%). The obtained
white power form copolymer dioxane, chlorine
hydrocarbon, dimethylsulphoxide when heated
in Na2CO3 solution is partially solved. IQ spec-
trum of synthesized copolymers has been re-
searched in 600–4000 cm-1 range in Bruker
spectrometry of Alfa firm. MST chains in the
copolymers are calculated according to acid
number.
The research of antimicrobial properties
of synthesized substances have been studied
with known method – dilution in series method
[4]. This was carried out with the following di-
lutions in sterile distilled water of 1% solution
prepared in dioxane (1:100, 1:200, 1:400,
1:800) (Table 1).

AZERBAIJAN CHEMICAL JOURNAL № 3 2017

18 THE RESEARCH OF ANTIBACTERIAL PROPERTIES OF METHYL METHACRYLATE…..

Table 1. Experimental indicators of radical copolymeriza- In experiments 1–2 drops of emulsion with
tion reaction of methylmethacrylate (M1) with methacrylo- 500 million microbs in 1 ml were dropped into
yl salicylate (M2); t=650C, solvent dioxane (75%), initiator
– benzoyl peroxide (0.2%), reaction time – 8 hours
every test glass. From every test glass during eve-
MST The amount ry 10–20 min planting has been carried out for an
The softe- hour.
amount in of MST
Yield, ning tem-
the mono- chains in the []
% perature, Results and their discussion
mer mix- copolymers, 0
C
ture, mas. % mas. % Corresponding absorption bands of the
0.0 0 88.6 0.82 110 synthesized copolymers in IQ spectra 1640–
5.0 4.7 75.7 0.75 112
1660 (C=C), 1745 (C=O), 1155 (C–O–C) and
10.0 8.8 74.5 0.56 117
25.0 21.6 62.5 0.48 122 3460 (O–H) cm-1 areas have been registered.
50.0 43.0 60.8 0.11 135 These results prove that the copolymers are in
the following structure and composition:
The effect of synthesized copolymers
was studied comparatively with ethanol, nitro-
fungin also dioxane. As test-culture the samples
CH 3 CH 3
from Grampositive microorganisms gold staph-
CH2 C CH2 C
ylococcus (St.aureas), as well as from gramneg-
atives coliforms (E.coli), from pigment form- C O C O .

ings blue-green pus bacillus and (Ps.aeru- OCH 3 O–

n
ginoza), from mushrooms Candida breed C.al- COOH m
bicans have been taken. In order to grow bacte-
ria FPA( fleshy pepton agar), for mushrooms
Saburo nutritious environment were used. The Antimicrobial effect of newly synthe-
plants were taken with 10, 20, 40, 60 minute sized polymer substances and controls are given
intervals, were kept for bacteria at 370C tem- in the Table 2.
perature for 24 hours in thermostat, for mush- As it is seen in the Table researched sub-
rooms kept at 280C temperature in were ther- stances effected various microorganism types
mostat for 48 hours. differently.

Table 2. Antimicrobial effect of synthesized polymer substances and controls

Examined substances Controls
Exposure time,

sample 1 sample 2
polymethyl-
5% methacryloyl 10% methacryloyl ethylene
min

Test culturas methacrylate dioxane nitrofungin

salicylate keeping salicylate keeping alcohol
(etalone)
copolymer copolymer
1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
10 – – + + – – – + – – + + – – + + – + + +
20 – – – + – – – + – – + + – – + + – + + +
St.aureus
40 – – – + – – – – – – – – – – – + – + + +
60 – – – – – – – – – – – – – – – – – + + +
10 – – – + – – – + – – – + – – – + + + + +
20 – – – + – – – + – – – + – – – + – + + +
Ps.aeruginoza
40 – – – + – – – + – – – + – – – + – + + +
60 – – – + – – – + – – – – – – – + – + + +
10 – – + + – – – + – – + + – – – + + + + +
20 – – – + – – – + – – – + – – – + – + + +
E. coli
40 – – – + – – – + – – – + – – – + – + + +
60 – – – – – – – – – – – + – – – + – + + +
10 – – – + – – – + – – – + – – – + + + + + + + + +
Candida 20 – – – + – – – – – – – + – – – + + + + + + + + +
albicans 40 – – – + – – – – – – – + – – – + – + + + – + + +
60 – – – – – – – – – – – – – – – + – + + + – + + +

AЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2017

 N.Sh.RASULZADEH et al. 19

But generally all synthesized substances
have antimicrobial effect. The synthesized sub-
stances themselves showed more active antimi-
crobial effect than dioxane they were solved in.
Thus, each of three substances showed more
active antimicrobial property against Gram-
positive microbs and Candida. For example: in
1:400 proportion methacryloyl salicylate with
methyl methacrylate copolymer (5%), polyme-
thyl methacrylate medicines destroyed St.aureus
during 20 min (there was end in control).
Each of three substances killed Candida
in 1:400 proportion for 10 min polymethyl
methacrylate medicine in 1:800 proportion for
20 min. In control end occurred in 1:800 pro-
portion even for an hour. Methacryloyl salicy-
late with methyl methacrylate copolymer (10%)
medicine killed Candida, also staphylococcus
and green pus bacillus in 1:800 proportion for
an hour.
It was defined from the results that re-
searched methacryloyl salicylate base copoly-
mers can be used both as bactericidal and fun-
gicides.
References
1. Kawabata N., Nishiguchi M. Antibacterial activity
of soluble pyridinium type polymers //Appl. Envi-
ron Microbial. 1988. T. 54. No 10. P. 2532–2535.
2. Rəsulzadə N.Ş., İbadov E.Ə., Abbasova A.Ç.
Akril və metakril turşularının salisil efirlərinin
sintezi və tədqiqi // Monomerlər və polimerlər
kimyasının müasir problemləri. III respublika
konfransının materialları. Sumqayıt, 05–06 noyabr
2015. S. 38.
3. Rəsulzalə N.Ş., Səfərova G.M., Şatırova M.İ.
Asetilsalisil turşusunun vinil efirinin sintezi və
tədqiqi // Monomerlər və polimerlər kimyasının
müasir problemləri. III respublika konfransının ma-
terialları. Sumqayıt, 05–06 noyabr 2015. S. 25.
4. Поздеев О.К. Медицинская микробиология:
Учебн. для вузов. / Под ред. Покровского В.И.
М.: ГЭОТАР МЕД, 2001. 768 с.

АНТИБАКТЕРИАЛЬНЫЕ СВОЙСТВА СОПОЛИМЕРОВ МЕТИЛМЕТАКРИЛАТА С

МЕТАКРИЛОИЛСАЛИЦИЛАТОМ
Н.Ш.Расулзаде, А.Г.Азизов , Е.А.Ибадов, С.К.Зейналова, Н.Ш.Расулов
Синтезированы и изучены антибактериальные свойства сополимеров метилметакрилата с метакрилоилсали-
цилатом различного состава. Определены минимальные ингибирующие концентрации (МИК) физиологических
растворов сополимеров, проявляющих антибактериальную активность в отношении бактерий St.aureus,
Ps.aeruginoza, C.Albigans, E.coli. Сополимеры, содержащие в своей цепи 5–10 мас.% салицилатных фрагментов,
проявляют более сильную антибактериальную активность (в 2–4 раза больше), чем полиметилметакрилат. Изу-
чены зависимости свойств сополимеров от состава исходной мономерной смеси.
Ключевые слова: сополимер, метакрилоилсалицилат, антибактериальные свойства.

METİLMETAKRİLAT VƏ METAKRİLOİLSALİSİLAT SOPOLİMERLƏRİNİN

ANTİBAKTERİAL XASSƏLƏRİNİN TƏDQİQİ
N.Ş.Rəsulzadə, A.H.Əzizov , E.Ə.İbadov, S.Q.Zeynalova, N.Ş.Rəsulov
Metilmetakrilatla metakriloilsalisilatın müxtəlif nisbətdə sopolimerləri sintez olunmuş və onların antibakterial xassələri
öyrənilmişdir. Sopolimerlərin və onların natrium duzunun fizioloji məhlullarının St.aureus, Ps.aeruginoza, C.albicans,
E.coli bakteriyalarına qarşı minimal inhibitor qatılığı (MİQ) təyin edilmişdir. Müəyyən olunmuşdur ki, tərkibində 5–10
kütlə % metakriloilsalisilat elementar üzvü saxlayan sopolimerlərin polimetilmetakrilata nisbətən antibakterial xassələri
2-4 dəfə yüksəkdir.
Açar sözlər: sopolimer, metakriloil salisilat, antibakterial xassələr.

AZERBAIJAN CHEMICAL JOURNAL № 3 2017