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CHEMICAL PROBLEMS 2023 no. 2 (21) ISSN 2221-8688
UDC 547.541:542.913
SYNTHESIS OF NEW THERMOSTABLE POLYHYDROXYESTER ON THE BASIS OF 2-HYDROXYPROPYL-1,3-BIS-CARBOXYMETHYLESTEROSULFOIMIDE OF SACCHARIN-6-CARBOXYLIC ACID
E.T. Aslanova, E.T. Mamedov, M.N. Rashidova, A.A. Garayeva, V.O. Atakishiyeva
Institute of Polymer Materials of the Ministry of Science and Education of the Republic of Azerbaijan,
S.Vurgun str, AZ5004, Sumgait, Azerbaijan e-mail:[email protected]
Received 17.03.2023 Accepted 11.04.2023
Abstract: By polycondensation of 2-hydroxypropyl-1,3-bis-carboxymethylesterosulfoimide of saccharin-6-carboxylic acid with ethylene glycol, a thermostable polyhydroxyester was obtained. The structure of the synthesized compound was confirmed by data of the infrared spectroscopy and the thermal stability studied by a method of differential-thermal analysis on a derivatograph of "Paulik—Paulik Erdei" system. The derivatographic investigations showed that the synthesized polyhydroxyester had high thermal stability and physical-mechanical properties.
Keywords: monomer, 2-hydroxypropyl-1,3-bis-carboxymethylesterosulfoimide of saccharin-6-carboxylic acid, polyhydroxyester
DOI: 10.32737/2221-8688-2023-2-140-145
Introduction
As is known, the polyesteroimides (PEI) are heterocyclic polymers, in which the aromatic rings are alternated with ester and imide groups. The high solubility of PEI favors the preparation of low-viscosity solutions with high polymer content. These solutions are used as lacquers. PEIs form the hard, elastic films stable to heat and possessing electrical isolating properties. A characteristic peculiarity of such films is their stability to simultaneous mechanical and thermal action [1].
As compared to aromatic PEIs, the aromatic polyesterosulfoimides (PESI) possess improved solubility, fire-, thermal- and radiation resistance [2,3].
Previously, the chloroanhydrides of disaccharindicarboxylic acid,
diesterosulfoimides [4, 5], dialkyl esters of N-carboxymethylsaccharin-6-carboxylic acid and diimides of disaccharindicarboxylic acid had been used as monomers for preparation of highly thermostable PESI in the polycondensation reaction with aliphatic and aromatic amines, diols and dichloroorganic
compounds.
There are data in the literature that the polyhydroxyesters (PHE) are characterized by such practically valuable properties as high adhesion to various surfaces, thermal stability, chemical resistance, low affinity to water. Owing to the free hydroxyl groups located along all length of the polymer chain, PHEs are able to cure, undergo the reaction with various substances - amines, acids, chloroanhydrides, etc. They are well combined with various organic and mineral fillers, which can be used for preparation of various polymer composites.
PHEs are valuable polymer materials used as the base of glues, lacquers, film-forming substances in a number of branches of technology. Unlike low molecular weight epoxypolymers, the high molecular weight ones are thermoplastic linear polymers with high content of the hydroxyl groups. The production of such polymers was mastered on an industrial scale in some countries [6-8].
All things considered, the aim of the work is the synthesis of new thermostable polymers
CHEMICAL PROBLEMS 2023 no. 2 (21)
www.chemprob.org
on the basis of sulfoimide-containing monomers.
With that consideration, we have
synthesized the sulfoimide-containing PHE by a method of polycondensation.
Experimental part
Synthesis of 2-hydroxypropyl-1,3-6is-carboxymethyl esterosulfoimide of saccharin-6-carboxylic acid. In a three-necked round-bottomed flask the mixture consisting of 25.5 g (0.05 mol) of 2-hydroxypropyl-1,3-èzs-esterosulfoimide of saccharin-6-carboxylic acid, 14 g (~0.1 mol) of powdered potassium carbonate, 9.5 g (~0.1 mol) of monochloroacetic acid and 50 g CI was dissolved in 260 ml of DMAA and boiled for 8 hours. Upon completion of the reaction, the obtained mass was cooled to room temperature; the fallen crystals were washed twice with DMAA and filtered through Schott filter. The synthesized substance was dried at room temperature and then in vacuum to a constant mass.
Synthesis of polyhydroxyester sulfoimide of saccharin-6-carboxylic acid. 12.52 g (0.02 mol) of 2-hydroxypropyl-1,3-ôw-carboxymethylesterosulfoimide of saccharin-6-carboxylic acid previously dissolved in 1.24 g (0.02 mol) of 1,2-ethanediol and 0.1 g of PbO was loaded into glass reactor equipped with a thermometer, a mechanical stirrer, a capillary and a nitrogen feeding pipe. The mixture was heated to 175 -180°C.
As a result of re-esterification, the methanol was isolated. Then, the temperature was raised to 220°C and the remaining methanol isolated for 1.5 hours. Upon completion of the reaction, the mass was washed with distilled water, and then the polymer was precipitated
firstly with ethyl alcohol, then with acetone. The obtained substance was dried under vacuum to a constant mass.
The physical-chemical properties of solvents were in line with the literature data [9, 10].
The infrared spectra were taken on the IR-Fourier spectrometers LUMOS and ALPHA (BRUKER Germany) in the wave frequency range 600-4000 cm-1, using the NPVO prefix with ZnSe crystal. The crystal diameter is 1 cm. A number of the sample scans is 24, the measurement duration is 30 sec.
The elemental analysis was carried out according the method [11] based on pyrolytic combustion of the organic substance in oxygen flow using the Pregl apparatus.
The thermal stability of the obtained compounds was studied by a method of differential- thermal analysis on derivatograph of Paulik-Paulik-Erdei system [12, 13]. Sample weighing - 200 mg, channel sensitivity TG-200, DTA-250 ^v, DTG -1 mv, temperature rise rate - 5°C/min in the air current.
Ostwald glass viscometers were used for measurement of the characteristic viscosity. The solvent flow time was from 46 to 120 sec. The concentration dependences of the reduced viscosity v rci /s = (t/ta — l)/s were
constructed for a number of samples. The Huggins constant values were determined by the slope of the experimental lines:
where k' - Huggins constant, which characterizes the thermodynamic interaction of the solvent and polymer, as well as the hydrodynamic behavior of the solution. The error of determination of [n] value does not
exceed 5 percent.
The study of physical-mechanical properties was carried out on a breaking machine WPM, VEB Thuringerindustriewerk, Rauenstein R-40, TYP-2092.
Results and discussion
The synthesis of new hydroxyl-containing sulfoimide of saccharin-6-carboxylic acid was polyesterosulfomide-polyhydroxyester (PHE) of carried out in two stages.
At the first stage, as a result of the 1,3-bz's-carboxymethyl esterosulfoimide of
interaction of 2-hydroxypropyl-1,3-bz's- saccharin-6-carboxylic acid (2-HP-1,3-bz's-
esterosulfoimide of saccharin-6-carboxylic acid CMES of S-6-CA) was synthesized according to
with monochloroacetic acid, 2-hydroxypropyl- the following scheme [14]:
r/oc-|
n
Il I _ I- ll_s0 / ^ —2HCI
\ o2s—-L ^J-Q-O-CH2-CH-CH2-O-C ^ S02
|| 2 I Z II
O OH
,—CO-
/ OC-.f^l
HOOCH2C-NV ^ 0 ^
2 \ 0-H2C—CH-CH2- o-
o
I
OH
.—CO-
Lso,/
N—CH2COOH
It revealed that the obtained product was a light coffee-colored powder, soluble only in aprotic solvents, such as DMFA, DMAA, DMSO, etc.
The yield of the purposeful product was
78.6 %.
The composition and structure of 2-HP-1,3-èz's-CMES of S-6-CA were determined by means of the elemental analysis and IR-spectroscopy.
Table 1. Physical constants of 2-HP-1,3-M?-CMES o
Compound Brutto formula Found,% Calculated, % MW M.p. °c Yield, %
C H N S
2-HP-1,3-èzs-CMES of S-6-CA C23H18O15N2S2 57.95 58.79 2.14 2.87 1.61 2.24 9.81 10.22 626 190 78.6
S-6-CA
It was established that in the IR spectra (Fig.1) of this compound there were absorption bands in the field of 1355, 1413, 1459 cm-1 of the deformation vibrations of C-H bond of CH2
group; valence vibrations of C=0-bond of acid groups in the field of 1721 cm-1; valence vibrations of COOH-group in the field of 2851, 2917 cm-1; valence vibrations of amide C = O-
bond in the field of 1679 cm-1; valence vibrations in the field of 1243, 1298 cm-1 of C-N-bond; valence vibrations of C-O- and O-H-bonds of alcohol in the fields of 1043 cm-1 and 3217 cm-1; valence vibrations of SO2-bond in the field of 1150, 1185 cm-1; deformation vibrations of C-H-bond (739, 861, 890 cm-1) of
substituted benzene ring [15-17].
At the second stage, by interaction of the obtained compound with ethylene glycol (1,2-ethanediol), new PHE of sulfoimide of saccharin-6-carboxylic acid has been synthesized according to the following scheme [18]:
HOOCH2C— N^
rrn
C-0-4i2C-CH-CH2-
Hriv
1—OC—H2C—N^
oc-
I
O OH
o
c-°-H2C-CH-CH2-'
ch2cooh + ho -(ch2)2-oh-m
-so;
CQ^N-CH2-C00-(CH2)z-0--
"-SO,
O
I
OH o
The yield of purposeful product was 77%.
It was established by IR spectroscopy that in the IR spectra of this compound there are absorption bands in the field of 2918 cm-1 of the deformation vibrations of C-H bond of CH2 group; valence vibrations (1107 cm-1) of C-0 bond of ester; valence vibrations of C=0-bond of acid groups in the field of 1726 cm-1; valence vibrations of amide C=0-bond in the field of
1644 cm-1; valence vibrations in the field of 1286 cm-1 of C-N-bond; valence vibrations of C-O- and O-H-bonds of alcohol in the field of 1052 and 3254 cm-1; valence vibrations of SO2-bond in the field of 1248; deformation vibrations of C-H-bond (761 cm-1) and valence vibrations of C-C-bond (1534 cm-1) of substituted benzene ring.
Fig. 2. IR spectrum of PHE of S-6-CA
It was experimentally proved that the viscosity of the obtained PHE of S-6-CA corresponds to [n]=0.62 dl/g.
It was established on the basis of differential-thermal analysis (DTA) data that the synthesized PHE was thermally stable in the
interval of 228-255°C and is well dissolved in polar aprotic solvents.
According to the physical-mechanical parameters, PHE has the following data: elongation, s - 5%, tensile strength, op - 105 MPa.
The synthesized PHEs of sulfoimide of thermostable coatings and films, as well as saccharin-6-carboxylic acid are of interest for polymer composites. their use in the production of glues,
References
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SAXARiN-6-KARBON TUR§USUNUN 2-HiDROKSiPROPiL-1,3-Jß/V-KARBOKSiMETiLEFiROSULFOiMiDi 9SASINDA YENi TERMiKi DAVAMLI
POLiHiDROKSiEFiRiN SiNTEZi
E.T. Aslanova, E.T. Mammadov, M.N. Ra^idova, А.Э. Qarayeva, V.O. Atakishiyeva
Azdrbaycan Respublikasi Elm vd Tdhsil Nazirliyinin Polmer Materiallari institutu AZ 5004, Sunqayit, S.Vurgun küg., 124 e-mail:[email protected]
Xülasa: Saxarin-6-karbon tur§usunun 2-hidroksipropil-1,3-bis-karboksimetilefirosulfoimidinin etilenqlikolla polikondensasiyasi naticasinda termiki davamli polihidroksiefir alinmi§dir. Sintez edilmi§ birla§manin strukturu iQ-spektroskopiya vasitasi ila tastiq edilmi§dir. Termiki stabillik "Paulik-Paulik-Erdey" sistemli derivatoqrafda differensial-termiki analiz üsulu ila öyranilmi§dir. Derivatoqraf tadqiqatlari göstarmi§dir ki, sintez edilmi§ polihidroksiefirlar yüksak termiki stabilliya va fiziki- mexaniki göstaricilara malikdirlar.
A?ar sözlar: monomer, saxarin-6-karbon tur§usunun 2-hidroksipropil-1,3-bis-karboksimetil-efirosulfoimidi, polihidroksiefir
СИНТЕЗ НОВОГО ТЕРМОСТОЙКОГО ПОЛИГИДРОКСИЭФИРА НА ОСНОВЕ 2-ГИДРОКСИПРОПИЛ-1,3-БИС-КАРБОКСИМЕТИЛЭФИРОСУЛЬФОИМИДА САХАРИН-6-КАРБОНОВОЙ КИСЛОТЫ
Э.Т. Асланова, Э.Т. Мамедов, М.Н. Рашидова, A.A. Гараева, V.O. Atakishiyeva
Институт Полимерных Материалов Министерства Науки и Образования
Азербайджанской Республики, ул. С Вургуна, 124, г. Сумгайыт, AZ 5004, Азербайджан e-mail:ipoma@science. az
Аннотация: Поликонденсацией 2-гидроксипропил-1,3 -бис-карбоксиметилэфиро-сульфоимида сахарин-6-карбоновой кислоты с этиленгликолем получен термостойкий полигидроксиэфир. Структура синтезированного соединения подтверждена данными инфракрасной спектроскопии. Термическую стабильность изучали методом дифференциально-термического анализа на дериватографе системы «Паулик-Паулик-Эрдей». Дериватографические исследования показали, что синтезированный полигидроксиэфир обладает высокой термостабильностью и физико-механическими показателями.
Ключевые слова: мономер, 2-гидроксипропил-1,3-бис-карбоксиметилэфиросульфоимид сахарин-6-карбоновой кислоты, полигидроксиэфир
