SU1578140A1 - Method of obtaining polyelectrolyte with groups of quarternary ammonium in side cirucit - Google Patents

Abstract

The invention relates to methods for producing polyelectrolytes with quaternary ammonium groups in the side chain and can be used in water treatment, in technology for producing emulsions, etc. The invention simplifies the technology for producing polyelectrolytes by reducing the number of stages and improving their performance properties (increasing the filtration coefficient to 12 , 4 .10 -6 cm / s at a concentration of the polymer in the solution of 0.05 wt.%). The effect is achieved through the use of ammonioacetylphenyl ethers of the formula X-OC (O) CH 2 -Y + CL-, where X is phenyl, 4-nitrophenyl, 4-bromophenyl, 3,4-dimethylphenyl

Y + is a pyridinium or dimethylbenzylammonium ion, as a modifier in the chemical modification of hydroxyl-containing polymers, preferably polyvinyl alcohol or starch at 40-50 ° C for 6-8 hours in water or an organic solvent in the presence of a tertiary amine. 1 hp f-ly, 1 tab.

Description

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The invention relates to the technology of obtaining water-soluble polymers and can be used in water treatment, the day of destruction by emulsion, etc.

The aim of the invention is to simplify the technology of polyelectrolyte production and improve their performance properties.

Example 1. Getting Modified | 01H agents.

but). Preparation of phenyl chloroacetate (PCA). 47.1 g of phenol (0.50 mol) and 22.0 g of NaOH (0.55 mol) are dissolved in 1000 ml of water, then with cooling and vigorous stirring, a solution of 43.7 ml (0.55 mol a) hporatsetn 1chporida in

150 ml of benzene. The precipitated phenyl chloroacetate is filtered off, washed with cold water (to pH 7 of the filtrate) and crystallized from isopropanol. Yield 78 g (91.5%).

Similarly, 4-nitrophenyl chloroacetate (NPHA), 4-bromophenyl chloroacetate (BFCA), and 3,4-dmethylphenyl chloroacetate (DMPCA) are obtained. At the second stage, the phenol | ilchloroacetate is quaternized with tertiary amines, fiiixofl 63-94%.

b). Preparation of Ј (phenyloxacarbonyl) methyl dimethylbenzylammonium chloride (FMDMBA).

To a solution of 34.12 g (0.2 mol) of phenylchloroacetate (PCA) in acetone (concentration 1.0 mol / l) was added 27.04 g (0.2 mol) of M, M-dimethylbenzylamine (DMBA) and stir at 45 ° C for 2.5 hours. The precipitate formed is filtered and washed with acetone. A practically pure white crystalline substance is obtained which is soluble in water and organic-water mixtures. Crystallized from methyl acetate. Yield 54.48 g (89%).

at). Preparation of Cphenyloxycarbonyl) MethylPiryridinium Chloride (FMP).

The synthesis is carried out in accordance with the procedure described in Example 16, but 15.82 pyridine is used instead of DMBA.

Similarly, chfyloxia is obtained through the use of , (4-bromophenyloxycarbonyl) methyl pyridium chloride (BFMP), L (3,4-dimethylphenyloxycarbonyl) methyl, dimethylbenzylammonium chloride (DMFDMBA), Ј (3,4-dimethylphenyloxycarbonyl) methyl pyridine chlorides, Ј (3,4-dimethylphenyloxycarbonyl) methyl pyridine chlorides, and

Example 2. 1.3 g (0.03 mol) of polyvinyl alcohol PVA is dissolved at 80-90 ° C in a mixture consisting of 5 (), 6 ml of dimethylacetamide and 2.4 ml (0.03 mol) of pyridine. The solution is cooled to 25 ° C and 10.3 g (0.03 mol) (4-nitrophenyloxycarbonyl) methyl dimethylbenzipammonium chloride is added. The molar ratio of components is 1: 1. Stir the reaction mixture

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After completion of the synthesis, the target product is precipitated with acetone, purified by supercooling from water, and dried under vacuum. Get modified PVA - white hygroscopic amorphous mass, yield 89% (relative to the initial amount of PVA). The degree of substitution is determined by the nitrogen content.

Found,%: C 58.34; H N 4.60.

Therefore, the degree of substitution is 47.5%, the static exchange capacity (SOY) is 3.28 mEq / g.

Example 3. Synthesis was carried out in accordance with the procedure described in Example 2, but (4-nitrophenyloxycarbonyl) methyl dipyridine chloride in the amount of 8.8 g (0.03 mol) was taken as a modifier: 1: 1, reaction temperature 45 ° C, time 7 hours

Exit 87%.

Found%: C 52.22, FI 6.64J N 5.81.

The degree of substitution is 51.5%, the EUC of 4.15 mEq / g.

EXAMPLE 4 The synthesis was carried out in accordance with the procedure described in Example 2, however, as a modifier, take B4-bromophenyloxycarbonyl) methyl dimechitbenzylammonium chloride in the amount of 11.5 g (0.03 mol) - the ratio is 1: 1, the reaction temperature is 45 ° С, the time is 7 h.

Yield 93%.

Found,%: C 58.17, H 8.29-; N 4.40.

The degree of substitution is 41.4%, SOY 3.14 mEq / g.

Example 5. The synthesis was carried out in accordance with the procedure described in Example 2, but using L (4-6poM-phenyloxycarbonyl) methyuG pyridium chloride in an amount of 9.9 g (0, 03 mol) as a modifier, the ratio is 1: 1, reaction temperature 45 ° C, time 7 hours

Yield 92%.

Found,%: C 52.57; H 6.41; N 5.49.

The degree of substitution is 44.3%, SOY 3.92 mEq / g.

Example 6. The synthesis is carried out in accordance with the procedure described in Example 2, however, in step 5.

As a modifier, take Cphenyl-oxycarbonyl) methyl dimethylbenzylammonium chloride in an amount of 9.2 g (0.03 mol) - 1: 1 ratio, reaction temperature 45 ° С, time — 7 h.

Exit 98%.

Found,%: C 58.03, H 8.50; N 4.28.

The degree of substitution is 38.2%, SOY 3.06 mEq / g.

Example 7. The synthesis was carried out in accordance with the procedure described in Example 2, however, as a modifier, take Ј (phenyl hydroxycarbonyl) methyl pyridium chloride in the amount of 7.5 g (0.03 mol) - 1: 1 ratio, the reaction temperature 45 ° C, time 7h.

Yield 96%.

Found: C, 52.64; H, 6.39; N, 5.21.

The degree of substitution is 38.9%, SOY 3.72 mEq / g.

Example 8. 7.7 g (0.048 mol of starch according to GOST 10163-76 is dissolved at 60-70 ° C in 96 ml of a mixture consisting of 92.1 ml of water and 3.9 ml (0.048 mol) of pyridine. The solution is cooled to 25 ° C and add 16.8 g (0.048 mol) Ј (4-nitrophenyloxycarbonyl) methyl dimethylbenzylammonium chloride. Reagent ratio 1: 1 based on the polymer unit. The reaction mass is stirred for 7 hours at 45 ° C, then filtered precipitated 4-NITROPHENOL, and the target product is precipitated with acetone, purified by reprecipitation from water and dried under vacuum.You get modified starch - white solid eschestvo, yield 109% (relative to the initial amount of starch).

Found,%: C 47.56; H 6.90; N 1.55.

The degree of substitution in relation to the elementary unit is 23.4%, the ESR of 1.11 mg-eq / g.

In the IR spectrum of modified starch, an intense absorption band is observed at 1755 (group).

Example 9. The synthesis was carried out in accordance with the procedure described in Example 8, with the difference that the loading of-(4-nitrophenyl-oxycarbonyl) methyl dimethylbenzylammonium chloride was 20.2 g

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(0.058 mol) - the ratio is 1: 1.2, the reaction temperature is 40 ° C, the time is 8 h. The yield is 111%.

Found,%: With 47.48 $ H 6.87; N G, 52.

The degree of substitution is 22.9%, SOY 1.09 mEq / g.

Example 10 (control). The synthesis is carried out in accordance with the procedure described in Example 8, however, the reaction is carried out at 30 ° C for 7 hours. Yield 102%.

Found,%: C 45.81, H 6.92 N 0.93.

The degree of substitution is 12.5%, SOY — 0.66 mEq / g.

Example 11 (control). Synthesis was carried out in accordance with the procedure described in Example 8, however, the reaction was carried out using 60 ° C for 7 hours. Yield 100%.

Found,%: C 44.95; H 6G77, N 0.64.

The degree of substitution is 8.2%, SOY 0.46 mEq / g.

Example 12. Synthesis was carried out in accordance with the procedure described in Example 8, however, {(4-nitrophenyloxycarbonyl) methyl, pyridinium chloride in an amount of 14.1 g (0.048 mol) is 1: 1 ratio taken as a modifier. The yield is 108%.

Found,%: C, 45.78; H 6.44, N 1.63.

The degree of substitution is 23.0%, SOY 1.16 mEq / g.

Example 13. The synthesis was carried out in accordance with the procedure described in Example 8, however, (4-bromophenyloxycarbonyl) methyl dimethylbenzylammonium chloride in an amount of 18.5 g (0.048 mol) is taken in a ratio of 1: 1 as a modifier.

The yield is 106%, the degree of substitution is 21.1%, the EOC is 1.02 mEq / g.

The proposed method allows to obtain water-soluble polyelectrolytes with ammonium groups in the side chain in one stage with a significant simplification of the technology. At the same time, the polymers do not contain gel fractions and because of this, they have improved operational properties, in particular, increased flocculating ability.

In tshgsit, data are given on the fluxing capacity (filtration coefficient values K. 10 cm / s) of hydroxyl-containing ionic polymers based on PVA and starch (the numbers of the examples correspond to the description of the invention) and their low and high molecular weight anapoids with respect to the joint precipitation of hydroxides titanium and bismuth.

Claims (2)

1. A method of producing polyelectrolyte with quaternary ammonium groups at a side price by chemically modifying a hydroxyl-containing polymer, characterized in that, in order to simplify the technology of polyelectrolyte production and improve its performance, modi-poly-p- (trimethyl-ammonium yl) styrene chloride "® filing is carried out by treatment with ammonium acetylphenyl ether form O - X 0-C-CHrY, C1 where X is phenyl, 4-nigrofenyl, 4-bromophenyl, 3, 4-dimethylphenig J is a pyridinium or dimethylbenzylammonium ion, at an equimolar ratio of hydroxyl containing polymer and ether in water of water or an organic solvent in the presence of a tertiary amine as a catalyst at 40–50 ° C for 6–8 h. 2. The method according to claim 1, about tl and h and u and with the fact that polyvinyl alcohol or starch is used as a hydroxyl-containing popimer.