PL196401B1 - New polyarylanes with lateral azo groups - Google Patents

Abstract

New polyarylates with pendant azo groups of the general formula 1, wherein R is a 2-thiazolyl group of the formula 2 or a benzothiazolyl group of the formula 3, wherein X is hydrogen or a CH3 group or a NO2 group.

Description

REPUBLIC

POLAND

Patent Office of the Republic of Poland (12) PATENT DESCRIPTION (19) PL (11) 196401 (13) B1 (21) Application number: 357227 (22) Application date: 20/11/2002 (51) Int.Cl.

C08G 63/68 (2006.01)

C08G 63/688 (2006.01) G01J 3/00 (2006.01) G02F 1/35 (2006.01) (54)

New polyarylates with pendant azo groups

(73) Patent holder: Warsaw University of Technology, Warsaw, Poland (43) Notification published: 31/05/2004 BUP 11/04 (72) Inventor(s): (45) The patent was granted on: Irmina Zadrożna, Warsaw, PL Krzysztof Kasiura, Warsaw, PL Marzena Arndt, Warsaw, PL Anna Kraska, Łochów, PL 31.12.2007 WUP 12/07 (74) Attorney: Joanna Bocheńska

⁽⁵⁷⁾ New polyarylates with pendant azo groups of the general formula 1, wherein R is a 2-thiazolyl group of the formula 2 or a benzothiazolyl group of the formula 3, wherein X is hydrogen or a CH3 group or a NO2 group.

PL 196 401B1

Description of the invention

The subject of the invention are new polyarylates with side azo groups of the general formula 1, wherein R is a 2-thiazolyl group of the formula 2 or a benzothiazolyl group of the formula 3, wherein X is hydrogen or a CH3 group or a NO2 group.

In the 1950s, methods for the synthesis and chemical modification of polymers made them an indispensable material for the production of polymer membranes and ion-exchange sorbents. The demand for membranes that are highly selective, mechanically and thermally stable, and whose properties are tailored to the composition and type of mixtures being separated led to the development of methods for forming membranes from virtually all industrially produced polymers. Currently, membranes are manufactured using polymers such as polyvinyl chloride, polyfluoroethylene, polyacrylonitrile, polypropylene, polyamides, polycarbonates, silicone rubber, and others. The number of industrial technologies employing polymer membranes and ion-exchange sorbents in component separation processes continues to grow.

New polyarylates with pendant azo groups exhibit second-order nonlinear susceptibility and may find applications in optoelectronics (optical fibers) and in the construction of devices doubling the frequency of electromagnetic waves (Burland D. M. Second Order Nonlinearity in Poled - Polymer, Chem. Rev., 1994, 94, 31 -75).

So far, appropriately substituted acrylates and methacrylates have been used to synthesize polymer systems with nonlinear optical properties. Currently, research is focused on polyarylates [I. Zadrożna: scientific papers, PW no. 67] and polyamides [W. Lang et al.: Macromolecules 2001, 34, 4774-79], polymers with high glass transition temperatures that determine the stability of optical properties. Unlike polyamides, the synthesis of polyarylates can be carried out at low temperatures, and the polymer itself is much easier to process using traditional methods.

Azo compounds are also known as the most numerous group of reagents used in spectrophotometric analysis. Methods using azo dyes are highly sensitive. Some azo reagents have been studied in more detail and have gained widespread use in analytical practice. Over the past decade or so, pyridyl azo dyes 1-(2-pyridylazo-2-naphthol) (PAN) and thiazolylazo dyes 4-(2-pyridylazo)resorcinol (PAR) have gained significant importance in spectrophotometric methods for metal determination. Thiazole azo compounds, such as the related PAR and PAN, exhibit similar properties as spectrophotometric reagents. Two representatives, 1-(2-thiazolylazo)-2-naphthol (TAN) and 4-(2-thiazolylazo)resorcinol (TAR), are among the most common in analysis.

Known azo compounds are obtained by coupling diazonium salts. Diazonium salts are obtained by diazotization, which involves the action of nitric acid (III) or alkyl nitrites on primary aromatic amine salts in a strongly acidic environment, due to the instability of nitric acid (III) and the resulting reaction product. Diazotization is usually performed at low temperatures (0-5°C). Coupling occurs readily in aqueous solutions and at low temperatures (approximately 0°C), but due to the weak electrophilic properties of diazonium ions, it is limited to aromatic compounds containing the most strongly activating groups in the ring, i.e., the amines of phenols, where the reaction mechanism is electrophilic aromatic substitution. The rate of coupling depends crucially on the pH of the solution, and the nature of this relationship is a consequence of the acid-base properties of phenols, amines, and diazonium cations.

Visible spectrophotometry is the most widely used instrumental method due to its high precision, sensitivity, and instrumentation availability. Spectrophotometric methods can be used to determine almost all elements over a wide range of concentrations and in any materials. The intensive development of spectrophotometric methods for determination, separation, and concentration of elements is closely linked to the development of complex chemistry. Many organic reagents form the basis of sensitive and selective spectrophotometric methods. The selectivity of color reactions and the corresponding spectrophotometric methods depends on the nature of the organic reagent used, the oxidation state of the elements, and the pH of the environment.

Palladium is a metal of considerable interest in both chemical analysis and organic synthesis due to its important role in the chemical and automotive industries, as well as its allergenic properties. This significant interest in this metal has resulted in a number of determination methods, depending on the palladium concentration (contents expressed in weight percent to nanograms) and the sample type (industrial, biological).

PL 196 401 B1

The most common palladium determination methods include spectrophotometric determination of palladium in the form of the Pdl4 ^2- iodide complex, and extractive determination with dimethylglyoxime or dithizone. Numerous methods for sorption of palladium in the form of the PdCl4 ^2- complex on cation and anion exchangers are also reported in the literature. Methods for sorption of palladium or palladium complexes on activated carbon, modified C18 silica gel, and polyurethane granules are also known. Palladium separation methods using liquid chromatography in the form of chloride complexes with PAN, 8-hydroxyquinoline, DDDTC, and aminophenol derivatives are also common. All methods involve Au, Hg, and Pt as interfering elements.

The new polyarylates with pendant azo groups according to the invention have a structure represented by formula 1, wherein R is a 2-thiazolyl group of formula 2 or a benzothiazolyl group of formula 3, wherein X is hydrogen or a CH3 group or a NO2 group.

The polyarylates according to the invention are obtained by a phase transfer catalytic polycondensation reaction between bisphenol A, azo compounds and tetra- and/or isophthalic chlorides in the presence of a catalyst which is tetraethylbenzylammonium chloride (TEBA-C1). The azo compounds used are those of the general formula 4, wherein R has the meaning given above.

Bisphenols are used in such molar ratios that the resulting polymer is soluble in the organic solvent in which the reaction is carried out.

New azo compounds are obtained by coupling appropriate diazonium salts with bis-2,2-(4-hydroxyphenyl)propane (bisphenol A) in solution, preferably acetic acid, in the presence of sodium acetate at 0-10°C, for several hours. The reaction is monitored using β-naphthol.

The obtained polyarylates show good solubility in chlorinated organic solvents.

₃

The limiting viscosity numbers of polyarylates are in the range of 0.312 - 2.080 [100 cm ³ /g]. The lowest value of the limiting viscosity number is found in the polymer with a 4% addition of a special monomer based on bisphenol A and 2-amino-6-methylbenzothiazole [PAR-19]. A general relationship was observed that with increasing percentage of the monomer - chromophore in the polymer, the value of the limiting viscosity number decreases, which indicates a low molecular weight.

New polyarylates have been obtained as selective analytical reagents.

The complexing properties of the resulting polyarylates with pendant azo groups on a solid sorbent with a high surface area were studied using UV/VIS spectroscopic methods. Based on the obtained absorption spectra, it was found that these compounds possess complexing properties. The formation of complexes with the following metal ions was studied: Cu ²⁺ , Co ²⁺ , Ni ²⁺ , Cd ²⁺ , and Pd ²⁺ . For {(4-(thiazolylazo)resorcinol)}, the formation of complexes with ions was observed. Cu ²⁺ , Co ²⁺ , {(4-(nitro-2-benzothiazolylazo)resorcinol} complexes Cu ²⁺ ions, {(4-(6-methyl-2-benzothiazolylazo)resorcinol forms complexes with such ions as. Cu ²⁺ , Cd ²⁺ , Ni ²⁺ , {bis 2,2-{5-nitrothiazolyl-(2-azo-4-hydroxyphenyl)propane) forms complexes with Cd ²⁺ ions, (bis 2,2-[3-(6-methylbenzothiazolyl-2-azo)-4-hydroxyphenyl)propane]} shows complexing properties towards Cu ²⁺ . The formation of complexes was influenced mainly by such factors as: pH of the reaction medium and temperature, surface area and type of sorbent. The azo compound obtained as {bis 2,2-(3-thiazolyl-2-azo-4-hydroxyphenyl)propane} (TAPHP) selectively complexes Pd ²⁺ from solution. It can therefore be concluded that it will be used as a selective spectrophotometric reagent in sensitive analytical methods.

The TAPHP polymer was deposited as a microfilm on a silica surface. Preliminary tests were conducted on the bed under dynamic conditions. The presence of palladium ions in a 0.1 mol x ^{1 -1} HCl environment resulted in a color change of the bed from yellow to brownish-red. This bed was also found to allow direct spectrophotometric measurements. The resulting bed was placed in a flow cell connected to a micro spectrophotometer. A beam of radiation was passed through the cell and delivered to the cell via an optical fiber. A second optical fiber received the signal and transmitted it to a detector. The column was washed with palladium solutions without platinum and with platinum in a Pd:Pt weight ratio of 1:1, 1:10, and 1:100. These measurements allowed for the generation of a standard curve representing the dependence of palladium mass on the signal value.

The new polyarylates according to the invention are presented in more detail in the embodiment examples.

Example I. In a 200 ml reaction flask equipped with a mechanical stirrer, 0.30 g (7.5 mmol) of NaOH in 20 ml of water is placed. Then a mixture of 0.660 g (2.88 mmol) of bisphenol A and 0.060 g (0.12 mmol) of bis 2,2-(3-thiazolyl-2-azo-4-hydroxyphenyl)propane (4%) is added. After bisphenol A and the dye have dissolved in the NaOH solution, 0.04 g (0.15 mmol) of

PL 196 401B1

TEBA-Cl dissolved in 5 ml of water. A solution of 0.415 g (2.03 mmol) of terephthaloyl chloride and 0.200 g (0.97 mmol) of isophthaloyl chloride in 30 ml of dichloromethane was placed in a pressure-equalizing dropping funnel and added dropwise over 20 minutes to the vigorously stirred solution. The reactor contents were stirred vigorously for approximately 2 hours. After this time, 30 ml of dichloromethane was poured into the flask and stirred for another 30 minutes. After this time, 2.5 ml of 5% HCl solution was added to the reaction mixture and stirring was reduced to prevent emulsion formation. After 30 minutes, the stirrer was turned off, and the aqueous and organic layers were separated. The organic layer was washed twice with water. The polymer was precipitated by pouring the polymer solution in dichloromethane into 90 ml of vigorously stirred acetone. The yellow, lumpy polymer was filtered and air-dried. 0.790 g of polymer was obtained, with a yield of 70%. Glass transition temperature Tg = 200°C. Initial decomposition temperature above 300°C.

¹ HNMR d=1.95 (s, 6H, CH3); 5.50 (bs, 2H, OH); 7.02-7.08 (m, 4H Artiazole); 7.66 (d, 2H, Ar, J=3.2 Hz); 7.90 (d, 2H, Ar, J=9 Hz); 8.05 (d, 2H, Ar, J=3.4H);

IR (KBr) 3432 (vOH); 1650 (vC=O); 1604 (vN=N) cm ^-1

The ultimate viscosity is 84.9 cm ³ /g.

Example II. The synthesis is carried out as in Example I, except that 0.645 g (2.82 mmol) of bisphenol A and 0.090 g (0.18 mmol) of bis 2,2-(3-thiazolyl-2-azo4-hydroxyphenyl) propane (6%) are used in the copolycondensation reaction. 0.820 g of yellow polymer is obtained in the form of compact lumps. Reaction yield: 71%. Ultimate viscosity: 118.7 ^cm3 /g. Tg= 202°C. Initial decomposition temperature: 300°C.

¹ HNMR d=1.89 (s, 6H, CH3); 5.30 (bs, 2H, OH); 7.02-7.08 (m, 4H Arthiazole); 7.58 (d, 2H, Ar, J=3.2 Hz); 7.93 (d, 2H, Ar, J-9 Hz); 7.88 (d,2H, Ar, J=3.4H);

IR (KBr) 3432 (vOH); 1650 (vC=O); 1604 (vN=N) cm ^-1

Example III. The synthesis was carried out according to the method described in Example I. 0.660 g (2.88 mmol) of bisphenol A and 0.065 g (0.12 mmol) of bis 2,2-{5-nitrothiazolyl-(2-azo-4-hydroxyphenyl)propane (4%) were used in the copolycondensation reaction. 0.750 g of an intense yellow polymer in the form of flocs was obtained. The reaction yield was 66%.

Tg= 203°C. Initial decomposition temperature 300°C.

¹ HNMR d=1.69 (s, 6H, CH3); 4.05 (s, 2H, OH); 6.78-7.13 (m, 4H, Ar); 7.99 (d, 2H, Ar, J=9.6 Hz); 8.79 (p, 2H, Artiazole);

IR (KBr) 3452 (vOH); 1655 (vC=O); 1592 (vN=N) cm ^-1

Example IV. The synthesis is carried out as in Example I. 0.670 g (2.94 mmol) of bisphenol A and 0.035 g (0.06 mmol) of bis 2,2 {5-nitrothiazolyl-(2-azo-4-hydroxyphenyl)propane (2%) are used in the reaction. 0.830 g of yellow, flocculent polymer is obtained with a yield of 74%. Intrinsic viscosity number 70.9 cm ³ /g. Tg= 205°C. Initial decomposition temperature 300°C.

¹ HNMR d=1.71 (s, 6H, CH3); 4.01 (s, 2H, OH); 6.75-7.10 (m, 4H, Ar); 7.89 (d, 2H, Ar, J=9.6 Hz); 8.81 (s, 2H, Arthiazole);

IR (KBr) 3452 (vOH); 1655 (vC=O); 1592 (vN=N) cm ^-1

Example V. The synthesis is carried out according to the method as in Example I. 0.670 g (2.94 mmol) of bisphenol A and 0.035 g (0.06 mmol) of bis 2,2-[3-(6-methylbenzothiazolyl-2-azo)-4-hydroxyphenyl)propane] (2%) are used in the reaction. 0.780 g of yellow polymer is obtained with a yield of 70%. Intrinsic viscosity 58.0 cm ³ /g. Tg= 211°C. Initial decomposition temperature 300°C.

¹ HNMR d=2.01 (s, 6H, CH3); 2.29 (s, 6H, CH3 thiazole); 3.15 (sb, 2H, OH); 7.09-7.40 (m, 6H); 7,797.97 (m, 6H, Arthiazole);

IR (KBr) 3352 (vOH); 1650 (vC=O); 1604 (vN=N) cm ^-1

Claims (1)

Patent claim New azo pendant polyarylates of the general formula I in which R is a 2-thiazolyl group of the formula II or a benzothiazolyl group of the formula III in which X is hydrogen or a CH3 group or a NO2 group.