SU1386624A1 - Method of producing copolymers containing chemically bound groups of dyestuff - Google Patents

Abstract

The invention relates to the field of polymer chemistry and can be used to create pH sensors operating in gas, water, and water-organic media. This is achieved by treating 1 g of chloromethylated cross-linked styrene copolymers of 0.5-2.0 g of phenolphthalein, bromophenol blue, xylenol orange in dimethylformamide in the presence of 0.00047-1.1 g of benzyltristhylammonium chloride and 0.856-5.20 g of potash during 6-8 h at 75-85 С, and the initial copolymer can be used in the form of a film, powder or fiber. 2 tab. (L

Description

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The invention relates to the chemistry of polymers, in particular to a method for producing copolymers containing chemically bound dye groups, and can be used to create pH-sensors of visual control.

The aim of the invention is to make the copolymers sensitive to changes in the concentration of hydrogen ions in air, in aqueous, organic and aqueous-organic media.

Example 1 In trihorls / th flask with a stirrer and reverse refrigeration

nichloride The reaction mixture is stirred and heated until 8 hours at this temperature, treated as in example 1.

The resulting copolymer has a bright orange color in the H-form at pH 1 7 and a purple color in Na -. form at pH 77. Conversion rate 0.8.

Example 4. In a three-necked flask with a stirrer and reflux condenser, 2.4 (0.01 mol) pieces of polypropylene-based film are placed with

lump placed 10 g (0.041 mol) of fiber 5 with twisted chloromethylated styrene

on the basis of polypropylene with grafted chloromethylated styrene (Ci 14.8%), 12.5 g (0.09 mol) are introduced - 1 g (0.0047 mol) benzyltriC, CO ,,

(CI 12%), 12.5 g (0.09 mol) of KiCOj, 0.0107 (0.000047 mol) of benzyltriethylammonium chloride, 1.91 g (0.006 mol) of phenolphthalein, 50 ml of di-

ethylammonium chloride, 20 g (0.063 mol) 20 methylformamide, 10 ml of ethyl alcohol

phenolphthalein, 240 ml of dimethylformamide, 50 ml of ethyl alcohol and 10 ml of HjO, stirred, heated to 75 ° C and kept for 6 hours at this temperature, 2 ml of distilled water, stirred, heated to 65-70 ° C and kept for 6 hours at this temperature. Then the film is removed, washed with water. Then the fiber is removed, washed out, extracted with ethanol.

wate with water, extract with ethanol.

The copolymer has a white color in the H-form at pH 7.8 and a bright crimson color at pH 9.0 s Na-form. The chlorine content in terms of dry matter C1 3,36i 0,01%. The molar conversion is 0.8.

Example 2. In a three-neck flask with a stirrer and reverse refrigeration

com 10 g (0.041 mol) of fiber-chloromethylated styrene in Example 1, 14 g (C1 13.5%) are introduced, 12.5 g (0.09 mol) are added

(0.1 mol), 5 g (0.0075 mol), 0.0107 g (0.000047 mol) of benzbromphenol blue, 50 ml of dimethylsiltriethylammonium chloride, 1.5 g of formamide, 45 ml of ethyl alcohol, ( 0.002 mol) bromophenol blue, 5 ml of water, 0.5 g (0.0022 mol) of benz-q zyltriethylammonium chloride. The reaction mixture is stirred and heated to 85 ° C, keeping at this temperature 10 MP of dimethylformamide, 10 ml of ethanol, 1 ml of distilled water. The reaction mixture is stirred and heated to 70-75 ° C, held at this temperature for 6 hours, and is treated as in Example 1.

round 8 h, treated in example 1.

The resulting copolymer has a bright blue to pH 2, in the range of pH 1.95-1.40 - green and at pH 3 1.3 - bright yellow. The chlorine content in terms of dry matter C1 4.8 + 0.01%. The molar conversion is 0.8.

Example 3. In a three-necked flask with a stirrer and a reflux condenser, 10 g (0.041 mop) of the fiber of Example 1 will be placed, 14 g (0.1 mol), 5 g (0.013 mol) of xylenol orange, 50 ml of dimethylformamide, 45 ml of ethyl alcohol, 5 ml of water and 0.5 g of benzyltriethylammo (CI 12%), 12.5 g (0.09 mol) of KiCOj, 0.0107 (0.000047 mol) of benzyltriethylammonium chloride, 1.91 g (0,006 mol) of phenolphthalein, 50 ml di-

one, 2 ml of distilled water, stirred, heated to 65-70 ° C and kept for 6 hours at this temperature. Then the film is taken out, washed. The film has a cloudy-white color at PX 67.5 and bright-purple at pH 9.0. The chlorine content in terms of dry matter Ci 2,8iO, 01%. The molar conversion is 0.8.

Example 5. In a three-necked flask with a stirrer and reflux condenser, 2.4 g (0.01 mol) of polypropylene-based powder with HB CO ,, 0.0107 g (0.000047 mol) of benzyltriethylammonium chloride, 1.5 g ( 0,002 mol) bromophenol blue, Q

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10 MP of dimethylformamide, 10 ml of ethyl alcohol, 1 ml of distilled water. The reaction mixture is stirred and heated to 70-75 ° C, held at this temperature for 6 hours, and is treated as in Example 1.

The resulting polymer has a blue color to pH 2, in the range of pH 1.95-1.40 - green, and at pH 5 - yellow. The chlorine content in terms of dry matter C1 4,35 ± 0,01%.

Example 6. In a three-necked flask with a stirrer and reflux condenser, 24.2 g (O, 1 mol) of the fiber of Example 1 were placed, 20.72 g (0.15 mol), 0.107 g (0.00047 mol) of benzyl were introduced. triethylammonium chloride, 19.1 g (0.06 mol) of phenolphthalein, 240 ml of dimethylformaquad, 50 MP of ethyl alcohol

that and 10 ml, stirred, heated to 75 ° C, incubated for 6 h and treated as in example 1,

The copolymer has a white color at pH 7.8 and bright magenta at pH

9.0. The molar conversion is 0.75.

Example 7. In a three-necked flask with a stirrer and reflux condenser, 24.2 g (0.1 mol) of the fiber of Example 1 were placed, 20.72 g (0.15 mol) of KjCO, 0.068 P (0.0003 mol) of benzyltriethylammonium were introduced. - chloride, 19.1 g (0.06 mol) of phenolphthalein, 240 ml of dimethylformamide, 50 ml of ethyl alcohol and 10 ml of 0, stirred, heated to 75 ° C, incubated for 6 hours, treated as in Example 1.

The copolymer has a white color at pH: 7.8 and at pH 9.0 is pink. The molar conversion is 0.5.

Example 8. In a three-necked flask with a fritter and reflux condenser, 24.2 g (0.01 mol) of the fiber of Example 1 were placed, 20.72 g (0.15 mol) of K, COe, 0.15 g (0, 00065 mol) benzyltriethylammonium chloride, 19.1 g (0.06 mol) of phenolft-leine, 240 ml of dimethylformamide, 50 ml of ethyl alcohol and 10 ml, stirred, heated to 75 s, incubated for 6 hours, treated as in example 1.

The copolymer has a white color at pH 7.8 and bright magenta at pH

9.0. The molar conversion is 0.8.

Yrimer 9. In a three-neck flask with a stirrer and reflux condenser, the reagents of example 8 are placed, stirred, heated to 60 ° C, kept for 6 hours, treated as in example 1.

The molar conversion is 0.45.

Example 10. The reagent flask with a stirrer and reflux condenser was placed in the reagents of example 8, stirred, heated to 90-95 ° C, held for 6 h, treated as in example 1.

The molar conversion is 0.82.

Conducting the reaction at a temperature below 75 ° C does not provide a satisfactory degree of conversion. When carrying out the reaction at a temperature above 85 ° C, no increase in the conversion is observed. Therefore, it is preferable to conduct the reaction in the temperature range of 75-85 C.

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Example 1. In a three-necked flask with a stirrer and reflux condenser are placed the reagents according to example 8, stirred, heated to 75 ° C, incubated for 4 hours, treated according to the example

RU 1.

The molar conversion is 0.3.

Example 12. In a three-neck flask with a stirrer and reflux condenser placed in the reagents of example 8, stirred, heated to 75 ° C, incubated for 12 h, treated as in example 1.

The molar conversion is 0.82.

Conducting the reaction for less than 6 hours does not allow a satisfactory degree of conversion to be obtained. Conducting a reaction. For more than 8 hours, no significant increase in conversion is obtained.

Example 13. 1 g of fiber obtained in Example I, having a bright crimson color, is placed in cones with an aqueous solution of hydrochloric acid and the change in color of the fiber is observed.

Example 14. 1 g of the fiber obtained in example 1 is placed in cones with an aqueous solution of alkali and ammonia, and a change in the color of the fiber is observed.

Example 15. 1 g of the fiber obtained in example 1 with a bright crimson color is placed in a flask with a mixture of freon (50 ml) and refrigerant oil (10 ml), 0.03 mg (0.0001 mol) of oleic acid. The original solution has a pH of 5.5. The fiber changes its color to white in 3-4 minutes.

The resulting copolymer has an intense bright color, convenient visual use, high mechanical strength due to the properties of the original copolymer, stable color reversibility in aggressive media due to the strong covalent bond of the chromogenic reagent with the copolymer and the chemical stability of the copolymer itself in aggressive media.

The properties of the copolymers are given in table. 1, data on the use of copolymers as pH indicators for the visual monitoring of the pH of the freon refrigeration machines are in table. 2

Claims (1)

Invention Formula The method of obtaining copolymers containing chemically bound groups 513 dyes by treating chemically methylated crosslinked styrene copolymers with dyes in a dimethylforma-MID medium, characterized in that, in order to make the copolymers sensitive to changes in the concentration of hydrogen ions in air, water, organic and water, medium, as chloromethylated Q bath crosslinked styrene copolymers, graft copolymer of polypropylene and chloromethylated styrene is used. 1 Bright Malinova HCi 0,001 and. -3.27 4-60 bela Bela HCL 0.01 n., 1 HCi 0.05 N.-1.35 HCi 0,1. N.-1,00 NaOHO, 05H., 2 NaOH 5 n. Bela Bright crimson five sinister Bela Dark red ka, parts pressure is 600 mm Er Mixture of freon 50 ml, chladone oil 10 ml and 0.03 mg of oleic acid Aqueous NaOH 5 n. Aqueous NaOH 5 n. II p and m e n and e. In examples 1, 4 and 6 use a graft copolymer with groups of phenolphthalein, in example 5 - a copolymer with groups of Bengal rose. Staining of the solution in examples 1-5 does not occur. In the form of a film, fiber or powder, a compound selected from the group consisting of phenolphthalein, bromophenol blue or xylene orange, taken in an amount of 0, 0 g per 1 g of copolymer is used as a dye, and the crosslinked polymer is processed in the presence of 0.00047-4), 1 g of benzyltriethylammonium chloride and 0,, 2 g of potash per 1 g of the copolymer at 7585 C for hours. I, one Table 0 bela 11 „0 Malinova 60 Rozova Malinova 2.5-3 2.0-2.5 2.0-2.5 1.5-2.0 1.5-2.0 1.0-1.5 2.0-2.5 2.5-3, O 1.0-1.5 ,five 60 Bela 3.0-4.0 60-360 Malinova , 0-1,5 60-360 Dark red Does not occur Cold-No. 113 + Bela 20 + 5% by weight of refrigeration oil, q.h. 0.02 Freon-113 + Bela 20 + 5 wt.% Of cold oil, k.ch. 0.05 table 2