Synthesis of polyhydroxyesters of sulphoimide sakharin-6-carbonic acid Текст научной статьи по специальности «Химические науки»



CHEMICAL PROBLEMS 2019 no. 4 (17) ISSN 2221-8688 571

UDC 547.54;583.2

SYNTHESIS OF POLYHYDROXYESTERS OF SULPHOIMIDE SAKHARIN-6-CARBONIC ACID

E.T. Aslanova

Institute of Polymer Materials National Academy of Sciences of Azerbaijan 124, S. Vurgun str., AZ 5004 Sumgayit, Azerbaijan; e-mail:elnara-aslanova@rambler.ru

Received 29.09.2019

Abstract: Heat-resistantpolyhydroxyesters were obtained through polycondensation of 2-hydroxypropyl-1,3-bis-ester of sulfoimide saccharin-6-carboxylic acid with some aliphatic diamines. Structures of the synthesized compounds were confirmed by infrared spectroscopy data. Thermal stability was studied by means of differential thermal analysis on a derivatograph of the Paulik-Paulik-Erdei system. Derivatographic studies showed that the synthesized polyhydroxyethers have a high thermal stability which decreases as a length of the aliphatic fragment in their composition increases. X-ray studies went to show that the obtained compounds were amorphous polymers. Keywords: saccharin-6-carboxylic acid, diamine, polyhydroxyether DOI: 10.32737/2221-8688-2019-4-571-575

Introduction

As is known, polyhydroxyethers (PHE) are characterized by practically valuable properties, specifically high adhesion to various surfaces, thermal stability, chemical resistance, low affinity for water. Owing to free hydroxyl groups located along the entire length of the polymer chain, PHE can cure and react with various substances - amines, acids, acid chlorides, etc. They are well combined with various organic and mineral fillers that can be used to obtain various polymer composites.

Note that PHEs are valuable polymeric materials used as the basis of adhesives, varnishes, film-forming substances in several engineering industries. In contrast to low molecular weight, epoxy polymers with high molecular weight are thermoplastic linear

polymers with a high content of hydroxyl groups. The production of these polymers has been commercialized in some countries [1, 2].

From the literature it is known that complex polyetherimides have high heat resistance and, unlike polyimides, are easily processed [3]. Compared to aromatic polyimides, aromatic polysulfoimides have an improved solubility, flame, thermal and radiation resistance [4-6].

Granting this, the purpose of the work is to synthesize new thermo-resistant polyhydroxyesters based on sulfoimide of saccharin-6-carboxylic acid.

On the basis thereof, we were the first to synthesize sulfoimide-containing PHE by means of polycondensation.

Experimental part

Materials. We used m-cresol ("Biochem", France); ethylenediamine (Neftegazkhimkomplekt LLC, Russia); tetramethylenediamine (Topan LLP, Kazakhstan); Hexamethylenediamine (Topan LLP, Kazakhstan); ethanol

(Bakikimyaeczasanaye LLC, Azerbaijan); acetone ("high purity", "Himmed Synthesis").

Synthesis of polyhydroxy esters of sulfoimide saccharin-6-carboxylic acid based on diamines. The flask was charged with 5.1 g (0.01 mol) of 2-hydroxypropyl-1,3-bis-ester-sulfoimide saccharin-6-carboxylic acid, 2.24 g (0.02 mol) of EDA-ethylenediamine, dissolved in 60 ml of m-cresol. The reaction mass, while stirring, was

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CHEMICAL PROBLEMS 2019 no. 4 (17)

heated at 160-170 ° C for 7 h. Then the mass was filtered, then washed with distilled water and besieged sequentially with ethanol and acetone; dried in vacuum to constant weight.

Polyethersulfoimides derived from tetramethylenediamine (2) and

hexamethylenediamine (3) were synthesized in the same way.

Physico-chemical properties of solvents were consistent with literature data [7].

Also, infrared spectra were recorded on a Fourier transform infrared spectrometer LUMOS (BRUKER company Germany) in a

wave frequency range of 600-4000 cm-1, using the ATR adapter with a ZnSe crystal. Crystal diameter is 1 cm. The number of sample scans is 24; measurement time is 30 seconds [8, 9].

The thermal stability of the obtained compounds was studied by means of differential thermal analysis on a derivatograph of the "Paulik-Paulik-Erdey" system [10, 11]. Sample weight is 200 mg, sensitivity of TG - 200, DTA - 250 ^v channels, DTG - 1 mv, temperature rise rate is 5° C / min in air flow.

Results and discussion

Synthesis of PHE of saccharin-6-carboxylic acid sulfoimide was performed on the basis of previously obtained 2-hydroxypropyl -1,3 -¿z's-ester-sulfoimide saccharin-6-carboxylic acid (2-HP-1,3-bis-ESIS-6-CA) incorporating ester and

OC

HN-

O2S

sulfoimide groups, as well as aliphatic diamines [12].

The polycondensation reaction of 2-HP-1,3-bz's-ESIS-6-CA with diamines was carried out in a solution of m-cresol at 160-170°C for 7 hours according to the scheme below:

NH2

c-o—CH2-O

C

H— CH2. OH

— O—C

O

NH +

I

R

I

nh2

- NH3

OC

—N-

O2S

C-^CH2-CH— CH2—O —C

O

C

NR

OH

O

where: R = (CH2)n , n = 2, 4, 6

n

It revealed that the IR spectra of the synthesized compounds contain absorption bands in a range of 1398, 1454 cm-1 deformation and 2852, 2922 cm-1 valence vibrations of C-H bond of the CH2 group; CH high-plane deformation (679, 750, 864 cm-1) vibrations of the substituted benzene ring; deformation (1457, 1628 cm-1) vibrations of the benzene ring; C-O stretching (1015 cm-1) vibrations of alcohol; stretching (1718 cm-1) C = O vibrations of the ester group; C-O stretching (1240 cm-1) vibrations of the ester bond; stretching (1156, 1340 cm-1) vibrations of SO2 groups; and C-N valence (1240, 1283 cm-1) vibrations. The broad and intense absorption band in a range of 3200-3550 cm-1 with a maximum of 3300 cm-1 refers to the stretching vibrations of associated hydroxyl

groups.

Phase state and morphology largely determine the physico-chemical properties of polymers, they are essential to understand processes in the course of operation and processing of materials [13]. There is no data on the phase state of PHE in the literature; therefore, the work in this area is of particular interest. Radiographic studies of PHE were performed using an automatic diffractometer of the "Drone" type (fig. 1) in the step-scan mode using X-rays with a wavelength of 1.7888A. The obtained X-ray patterns revealed in all samples of synthesized PHE the presence of amorphous ring while the absence of peaks in the crystalline phase allows us to define them as completely amorphous polymers. As an example, Fig. 1 shows that the radiograph of

polyhydroxyester of sulfoimide of saccharin-6- of tetramethylendiamine. carboxylic acid was synthesized on the basis

Fig. 1. Radiograph of polyhydroxyesters of sulfoimide of saccharin-6-carboxylic acid synthesized on the basis of tetramethylendiamine

According to the differential thermal polar aprotonic and phenolic solvents. analysis (DTA) data, it found that the The characteristics of PHE (1-3) is

synthesized PHEs are thermo-stable in the given in Table 1. range of 237-265°C and are well soluble in

Table 1. Some characteristics of polyhydroxyesters of composition 1-3.

Polymer Output, % M*, dl/g Softening temperature, °C Decomposition starting temperature, °C

1. 70.0 0.55 235 265

2. 72.0 0.60 223 250

3. 75.0 0.67 215 237

*0.5 g of polymer in 100 ml of DMF at 40°C

As is seen from Table 1, the obtained compounds can be arranged in terms of thermal stability depending on the used diamine: ethylenediamine

(1)>tetramethylenediamine (2)>

hexamethylenediamine (3).

Note that synthesized PHE of sulfoimide saccharin-6-carboxylic acids are of interest from standpoint of their use in the production of adhesives, heat-resistant coatings and films.

References

1. Beeva D.A., Mikitaev A.K., Beev A.A., Olkhovaya G.G. Bisphenol-based polyhydroxy ethers synthesis. Sovremennye naukoemkie Tehnologii - Modern high-tech technologies, 2004, no.1, pp. 81-82 (In

Russian).

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polyhydroxyether. Vestnik Donbasskoj Nacional'noj Akademii stroitel'stva i

arhitektury - Bulletin of the Donbass National Academy of Civil Engineering and Architecture. 2014, no.l (105), pp. 133-138 (In Ukraine).

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5. Aslanov T.A. Synthesis of polyamido(ether)sulfimides by polycondensation. Azerbaijan Chemical Journal, 2005, no. 4, pp.116-122.

6. Aslanov T.A., Mamedaliyeva F.M., Ishenko N.Ya., Aslanova E.T., Mamedov B.A. Thermostable epoxide compositions on the basis of aromatic diamidodisulfoimide resins. Chemical problems, 2010, no. 3, pp. 490-492.

7. Gordon A., Ford R. Sputnik khimika. Moscow: Mir Publ., 1976, 546 p. (In

Russian).

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11. Kurenkov V.F. Workshop in chemistry and physics of polymers. Moscow: Himija Publ., 1990, 299 p. (In Russian).

12. Aslanova E.T., Aslanov T.A., Mammadova A.A., Mammadov B.A., Nurullayeva D.R. Synthesis of 2-hydroxypropyl -1,3 -bis-esterosulphoimides of saccharin-5- and -6-carboxylic acid. Azerbaijan Chemical Journal, 2018, no. 4, pp. 45-47.

13. Tugov 1.1., Kostrykina G.I. Chemistry and physics of polymers. Moscow: Himija Publ., 1989, 432 p. (In Russian).

SAXARiN-6-KARBON TUR§USUNUN SULFOiMiDiNiN POLiHiDROKSiEFiRLdRiNiN

SiNTEZi

E. T. Aslanova

Azarbaycan Milli Elmlar Akademiyasi Polimer Materiallari institutu AZ 5004, Sumqayit, S.Vurgun kuçasi, 124 E-mail: elnara-aslanova@rambler.ru

Saxarin-6-karbon turçusunun 2-hidroksipropil-1,3-bis-efirosulfoimidinin bazi alifatik diaminlarla polikondenslaçdirilmasindan termiki davamli polihidroksiefirlar alinmiçdir. Sintez olunmuç birlaçmalarin quruluçu infraqirmizi spektroskopiya usulu ila tasdiq edilmiçdir. Termiki stabillik differensial-termiki analiz usulu ils "Paulik-Paulik-Erdey" sistemli derivatoqrafda ôyranilmiçdir. Derivatoqrafik tadqiqatlar gôstardi ki, sintez olunmuç polihidroksiefirlar yuksak termiki stabilliya malikdirlar, onlarin termiki stabilliyi tarkibindaki alifatik fraqmentin uzunlugu artdiqca azalir. Rentgenoqrafik tadqiqatlarla subut edilmiçdir ki, alinmiç birlaçmalar amorf polimerlardir. Açar sôzldr: saxarin-6-karbon turçusu, diamin, polihidroksiefir

СИНТЕЗ ПОЛИГИДРОКСИЭФИРОВ СУЛЬФОИМИДА САХАРИН-6-КАРБОНОВОЙ КИСЛОТЫ

Э.Т. Асланова

Институт Полимерных Материалов Национальной АН Азербайджана AZ 5004 Сумгайыт, ул. С. Вургуна, 124 E-mail: elnara-aslanova@rambler.ru

Поликонденсацией 2-гидроксипропил-1,3-бис-эфиросульфоимида сахарин-6-карбоновой кислоты с некоторыми алифатическими диаминами получены термостойкие полигидроксиэфиры. Структуры синтезированных соединений подтверждены данными инфракрасной спектроскопии. Термическую стабильность изучали методом дифференциально-термического анализа на дериватографе системы «Паулик-Паулик-Эрдей». Дериватографические исследования показали, что синтезированные полигидроксиэфиры обладают высокой термостабильностью, уменьшающейся по мере роста длины алифатического фрагмента в их составе. Рентгенографическими исследованиями доказано, что полученные соединения являются аморфными полимерами. Ключевые слова: сахарин-6-карбоновая кислота, диамин, полигидроксиэфир