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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 1 2023 ISSN 0005-2531 (Print)
UDC 547.54; 583.2
SYNTHESIS OF SUPER-BRANCHED POLYGLYCERIDES OF SACCHARIN-6-CARBOXYLIC ACID
E.T.Aslanova, M.N.Rashidova, A.A.Garayeva, S.Y.Heydarova
Institute of Polymer Materials, Ministry of Science and Education of the Republic of Azerbaijan
Received 19.05.2022 Accepted 19.07.2022
By polycondensation of triglyceride of saccharin-6-carboxylic acid with some aliphatic diamines, the thermal-stable super-branched polyestersulfoimides - polyglycerides of saccharin-6-carboxylic acid have been obtained. The structures of the synthesized compounds have been confirmed by data of the IR spectroscopy. The yield of the purposeful product was 80-83%. It has been found that the synthesized polyglycerides are well dissolved in polar aprotonic solvents. The thermal stability of the obtained compounds was studied by a method of differential-thermal analysis on derivatograph of system "Paulik-Paulik-Erdey". The derivatographic investigations showed that the synthesized polyglycerides have high thermal stability, decreasing with the growth of length of the aliphatic fragment in their composition. For comparative estimation of the thermal and physical-mechanical indices of the synthesized poly-glycerides, the corresponding indices of the industrial polyesterimide Zellamid 1000 have been also given. It has been found that the obtained polyglycerides do not concede to industrial polyesterimides on physical-mechanical indices, but exceed them on thermal stability.
Keywords: saccharin-6-carboxylic acid, diamine, polyglyceride.
doi.org/10.32737/0005-2531-2023-1-83-89 Introduction
It was known that the polyesterimide (PEI) are heterocyclic polymers, in which the aromatic rings are alternated with ester and im-ide groups. The high solubility of PEI favors the preparation of low-viscous solutions with high polymer content. Such solutions are used as lacquers. PEI form strong, elastic films stable to heat and possessing electrical-isolating properties. The characteristic peculiarity of such films is their resistance to simultaneous mechanical and thermal effects [1].
bis-Imidodicarboxylic acids are widely used for the synthesis of PEI [2], which allows to change considerably the properties of polymers due to introduction of various groups -aliphatic, fatty aromatic, cyclic, etc. into the composition of the molecule. The formation of PEI in this case proceeds in one stage in the melt or in solution and is subjected to the regularities of the esterification reaction [3].
In comparison with aromatic PEI, the aromatic polyestersulfoimides (PEI) have improved solubility, fire-, thermal- and radiation resistance [4, 5].
Previously, for preparation of highly thermal-stable PESI in the polycondensation reaction with aliphatic and aromatic amines, diols and dichloroorganic compounds, the chloroa-nhydrides of disaccharindicarboxylic acid, diesterosulfoimides [6, 7], dialkyl esters of N-carboxymethylsaccharin-6-carboxylic acid and diimides of disaccharindicarboxylic acid have been used as monomers.
It was known from the literature that the branching of the polymer chain shows a strong influence on many macroscopic properties of polymers (viscosity of their solutions and melts, thermal stability, processing temperature, etc.). It has been established that the characteristic viscosity of branched polymers is several times less than the characteristic viscosity of linear polymers of the same molecular weight [8]. Now, new low-viscous and low-shrinkage den-drite-like super-branched aliphatic and aromatic polyesters have been synthesized [9, 10]. The attention to polymers of super-branched structure, besides exclusively scientific-fundamental interest, has been stipulated by the large practi-
cal significance shown by the use of super-branched polymers in various branches of industry [11, 12]. The availability of a large quantity of end functional groups in its composition enables the further changes of super-branched polymers for giving them the properties required in creation various kinds of materials [13].
It was also known that during carrying out of polycondensation in the presence of one or more compounds with more than two functional groups, the branched polymer is obtained [14].
In this paper the polycondensation reaction of triglyceride of saccharin-6-carboxylic acid with the formation of super-branched polyes-terimides - polyglycerides of saccharin-6-carboxylic acid (PGS-6-CA) is described.
The purpose of the work is the synthesis of new thermal-stable elastic polymers on the basis of branched sulfoimide-containing monomers.
Experimental part
Materials. In work we have used m-cresol (LLC"Biochem", France); ethylenedi-amine (LLC"Neftegazkhimkomplekt", Russia); tetramethylenediamine (LLP"Topan", Kazakhstan); hexamethylenediamine (LLP "Topan", Kazakhstan); ethanol (LLC"Bakukimyaezazse-naye", Azerbaijan); acetone (special purity grade, "Himmed Synthesis"), distilled glycerine (GOST 6824-96, mark PK 94, Russia).
Synthesis of triglyceride of saccharin-6-carboxylic acid by reesterification of aliphatic esters of sulfoimide of saccharin-6-carboxylic acid with glycerine. A mixture of 40 g (0.016 mol) of ethyl ester of saccharin-6-carboxylic acid, 7.5 g of PbO in 4.6 g (0.05 mol) of 1,2,3-propanetriol (glycerine) was heated to 115-1170C with stirring for 2 hours. The reaction mass was dissolved in DMFA and isolated with distilled water. The obtained powdery product coffee-milk colour was dried at room temperature and brought to constant weight in vacuum. M.p. =1670C.
Synthesis of polyglycerides of sac-charin-6-carboxylic acid on the basis of dia-mines. 7.2 g (0.01 mol) of triglyceride of sac-
charin-6-carboxylic acid, 3.36 g (0.02 mol) of ethylenediamine and dissolved 65 ml of m-cresol were loaded into the flask. Stirring the reaction mass was heated at 170-1800C for 8 h. Then the mass was filtered, washed with distilled water, precipitated sequentially with ethyl alcohols and acetone and dried in vacuum to a constant mass.
PGS-6-CA, obtained on the basis of tet-ramethylenediamine(2) and hexamethylene-diamine (3) have been similarly synthesized.
The physical-chemical properties of the glycerine and solvents corresponded to the literature data [15].
The infrared spectra were taken on IR-Fourier - spectrometer LUMOS ((BRUKER, Germany) in the wave frequency range of 6004000 cm-1, using the attachment NPVO with ZnSe crystal. The crystal diameter - 1 cm. The number of sample scans - s 24, the measurement duration is 30 sec. [16, 17].
The thermal stability of the obtained compounds was studied by a method of differential-thermal analysis on a derivatograph of "Paulik-Paulik-Erdei" system [18, 19]. The sample weight - 200 mg, sensitivity of channels - TG-200, DTA-250 mv, DTG-1 mv, temperature rise rate - 50C/min. in 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 nsp/c = (t/t0 - 1)/s were constructed for a number of samples. The Huggins constant values were determined by the slope of the experimental straight lines:
nnp/c=[n]+k-[n]2-c,
where c' - Huggins constant, which characterizes the thermodynamic interaction of the solvent and polymer, as well as the hydrodynamic behavior of the solution. The value determination error of [n] does not exceed 5 percent.
The study of physical-mechanical properties was carried out on a breaking machine
WPM, VEB Thuringerindustriewerk, Rauen-stein R-40, TYP-2092.
Results and discussion
The process of synthesis of polyglyce-rides of saccharin-6-carboxylic acid was carried out in two stages.
At the first stage, a triglyceride of saccha-rin-6-carboxylic acid, having ester and sulfo-imide groups in its composition has been obtained [20]. The synthesis was carried out by reesterification of alkyl esters of sulfoimide of saccharin-6-carboxylic acid with 1,2,3-pro-pantriol (glycerine) according to the following scheme:
nr
-co
\
CH2-CH-CH2
PbO
3 R-OOC-!^^"\so/nh + OH OH OH -3ROH
HN/OCnr^l f^II' ;nh
\ o2s—-L ^-C- 0-CH2-ÇH—CH2— O-C—^ J-—so2/ ^^ II I ^^
n-co-
o
h
\
o
HI
oc^o2
NH
R— -CH3, -C2H5, -C3H7
The obtained product is a powder of light-coffee-milk colour, soluble only in aprotic solvents such as DMF, DMAA, DMSO, etc.
The composition and structure of the obtained compound has been determined by elemental analysis and IR spectroscopy.
In the IR spectra of the obtained compound (Figure 1), the following absorption bands were observed: deformation (720, 395, 1454 cm-1) and valence vibrations of C-H bond of CH2 groups; valence vibrations (1644 cm-1)
of C=O bond of the amide; valence vibrations (1719 cm-1) of C=O bond of the ester; valence vibrations (1153 cm-1) of C-O bond of the ester; valence vibrations (1239, 1283 cm-1) of SO2 group; valence vibrations (1019 cm-1) of S=O bond; deformation (1573 cm-1) and valence vibrations (3276 cm-1) of N-H bond; deformation vibrations (617, 678, 750, 859, 1607 cm-1) of C-H bond of the substituted benzene ring.
Table 1. Physical constant of triglyceride of saccharin-6-carboxylic acid synthesized by one-stage method
Compound Brutto formula Found,% Calculated, % M T 0C T m, c Yield, %
C H N S
Triglyceride of saccha-rin-6-carboxylic acid C27H17015N3S3 44.98 45.06 2.46 2.36 5.79 5.84 13.31 13.35 719 167 67
Fig. 1. IR spectrum of triglyceride of saccharin-6-carboxylic acid.
The synthesis of polyglycerides of saccharin-6-carboxylic acid was carried out according to the following scheme:
HN<1°CT |1 „ „ i T^NH + NH2-R-NH2
sOj-1^^—C-O-CHj-CH-CHr-O-C-'l^J— SOf 2 2 "2NH3
:=o
where: R = (CH2)n , n = 2, 4, 6
Yield of purposeful product - 80-83%.
In the IR spectra of the obtained compound (Figure 2), the deformation bands in the field of 1385, 1438, 1485 cm-1 of C-H-bond of CH2 groups; valence vibrations of C=O bond of amide (1643 cm-1); valence vibrations of C=O bond of ester (1719 cm-1); valence vibrations of C-O-bond of ester (1108, 1129, 1147, 1168 cm-1); valence vibrations (1252, 1277 cm-1) of SO2-group; deformation (1553 cm-1) and valence (3268, 3352 cm-1) vibrations of N-H-bond; deformation (674, 694, 713, 757, 788, 829, 867, 607 cm-1) vibrations of C-H-bond of substituted benzene ring are appeared.
It has been established according to the data of differential-thermal analysis (DTA) that the synthesized PGS-6-CA are thermostable in the range of 268-2800C and are well soluble in polar aprotic solvents. For comparative
estimation of the thermal indices of the synthesized polyglycerides, the corresponding indices of the industrial polyesterimide Zellamid 1000 have been also given. The comparative technical characteristics of PGS-6-CA (1-3) and Zellamid 1000 are presented in Table 2.
As can be seen from Table 2, PGS-6-CA has a low viscosity, which is typical for super-branched polymers, but at the same time they are stable up to 268-2800C. On thermal stability, the obtained compounds depending on the used diamine are located in the following series: ethylenediamine (1) > tetramethylenediamine (2) > hexamethylenediamine (3). On physical-mechanical parameters, PGS-6-CA concedes to industrial polyesterimides, and on thermal stability exceed them (Table 3).
Fig. 2. IR spectrum of polyglyceride of saccharin-6-carboxylic acid. Table 2. Some characteristics of polyglycerides of composition 1-3
Polymer Yield, % M*, dl/g T • T besin. soften.., c T • T begin decomp., c
1. 83.0 0.18 255 280
2. 83.0 0.16 247 275
3. 80.0 0.15 245 268
Zellamid1000 — 0,20 170 197
Table 3. Physical-mechanical indices of polyglycerides of composition 1-3
Polymer Tensile strength, oD., MPa Specific elongation, e, %
1. 100 4.5
2. 110 5.0
3. 115 5.5
Zellamid1000 110 5,5
Conclusions
The new thermal-stable super-branched polyestersulfoimides - polyglycerides of sac-charin-6-carboxylic acid have been synthesized.
It was found that the obtained poly-glycerides are well dissolved in polar aprotic solvents. It has been established that the synthesized compounds have high thermal stability, decreasing on the length growth of the aliphatic fragment in their composition. For comparative estimation of the thermal and physical-mechanical indices of the obtained polyglycer-ides, the corresponding indices of the industrial polyesterimide Zellamid 1000 have been also given. It has been found that the synthesized compounds do not concede to industrial polyes-terimides on physical-mechanical indices, but exceed them on thermal stability.
The synthesized PGS-6-CAs is of interest for their use in the production of glues and heat-resistant coatings.
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SAXARiN-6-KARBON TUR§USUNUN YUKSЭK §AXЭLЭNMi§ POLIQLiSERiDLЭRiNiN SiNTEZi
E.T.Aslanova, M.N.Rэ§idova, A.Э.Qarayeva, S.Y.Heydэrova
8ахапп-6-кагЬоп tur§usunun trigliseridinin тиэууэп alifatik Шатт1эг1э polikondensasiyasl nэticэsindэ termikidavamll yuksэk §ахэ1эпт1§ poliefirsulfoimidlэr - 8ахаг1п-6-кагЬоп tur§usunun poligliseridlэri allnml§dIr. Sintez edilmi§ Ьи-к^экт^т 8й-цкШг1ап infraqlrmlzl spektroskopiya vasitэsi1э tэsdiq ейПт^йш Hэdэf о1ипап тэИ8и1ип mэhsuldarllgl 80-83 faiz tэ§kil edib. Миэууэп ейПт^йи- к1, sintez edilmi§ poliqliseridlэr ро1уаг aproton hэ11edici1эrdэ yax§l hэ11 О^ПШ^. Alшan Ьи-к^э^т^т termikidavamllllgl Paulik-Pau1ik-Erdey sistemli derivatoqrafiyasmda diferensial-termiki ana1iz1э tэdqiq е&^з&г. Derivatoqrafik tэdqiqatlar gбstэrmi§dir Ы, sintez edilmi§ poliqliseridlэr yuksэk termikidavamllga malikdirlэr, hansl ki, onlarIn tэrkibindэki a1ifatik fraqmentin artdlqca azallr. Sintez edilmi§
po1iq1iserid1эrin termiki уэ fiziki-mexaniki xassэ1эrinin muqayisэ1i qiymэt1эndiri1mэsi Д^ИП sэnaye po1ieterimid Ze11amid 1000-in muvafiq parametrlэri dэ verilmi§dir. Mэlum olmu§dur ki, alInan poliq1iserid1эr fiziki-mexaniki gбstэrici1эrinэ gбrэ sэnaye po1iefirimid1эrdэn geri qalmlr, termikidavamlIhgma gбrэ onlarI ustэ1эyir.
Адаг sбzlэr: saxarin-karbon Шг§ши, diamin, poliqliserid.
СИНТЕЗ CВЕРХРАЗВЕТВЛЕННЫХ ПОЛИГЛИЦЕРИДОВ САХАРИН-6-КАРБОНОВОЙ КИСЛОТЫ
Э.Т.Асланова, М.Н.Рашидова, А.А.Гараева, С.Я.Гейдарова
Поликонденсацией триглицерида сахарин-6-карбоновой кислоты с некоторыми алифатическими диаминами получены термостойкие сверхразветвленные полиэфирсульфоимиды - полиглицериды сахарин-6-карбоновой кислоты. Структуры синтезированных соединений подтверждены данными инфракрасной спектроскопии. Выход целевого продукта составил 80-83%. Выяснено, что синтезированные полиглицериды хорошо растворяются в полярных апротонных растворителях. Термическую стабильность полученных соединений изучали методом дифференциально-термического анализа на дериватографе системы "Паулик-Паулик-Эрдей". Дереватографические исследования показали, что синтезированные полиглицериды обладают высокой термостабильностью, уменьшающейся по мере роста длины алифатического фрагмента в их составе. Для сравнительной оценки термических и физико-механических показателей синтезированных полиглицеридов также приведены соответствующие показатели промышленного полиэфиримида Ze11amid 1000. Было выяснено, что по физико-механическим показателям полученные полиглицериды не уступают промышленным полиэфиримидам, а по термостойкости превосходят их.
Ключевые слова: сахарин-6-карбоновая кислота, диамин, полиглицерид.
