RU2213063C1 - Method for preparing bactericidal preparation - Google Patents

Abstract

FIELD: organic chemistry, medicine. SUBSTANCE: invention relates to technology for preparing bactericidal polyhalide salts of organic compound, in part, quaternary ammonium bases. Method for preparing a bactericidal preparation involves treatment of ion-exchange resin based on quaternary ammonium base with iodine-containing solution. Solution is prepared by iodine dissolving in 0.1- 0.4% alcoholic alkali and treatment is carried out up to preparing the bactericidal preparation of the general formula: R₄NJ_n•((n-1)/2)•H₂O wherein n is a whole uneven number from 3 to 9; R is an organic radical; N is nitrogen atom; J is iodine atom. Except for, for preparing bactericidal preparation of the general formula: R₄NJ₉•4H₂O resin treatment is carried out up to complete saturation of resin with iodine. For preparing bactericidal preparation of the general formula: R₄NJ_n•((n-1)/2)•H₂O wherein n = 3, 5, 7 iodine solution in alcoholic alkaline is prepared on the basis of stoichiometric ratio in the range 0.5-1.2 of iodine per 1 g of resin and treatment of resin with solution is carried out up to the complete absorption of iodine by resin. After treatment resin is washed out with potassium or sodium iodide concentrated solution and then with deionized water up to negative reaction for free iodine. Processes of treatment and washing out are repeated. Except for, treatment of resin with iodine-containing solution is carried out at temperature 15-40 C. Prepared composition based on quaternary ammonium base polyiodides shows the improved bactericidal properties and does not form toxic products. Invention can be used for creature of effective disinfecting agents using for water and aqueous solutions. EFFECT: improved preparing method. 5 cl, 2 tbl, 2 ex

Description

 The invention relates to the field of chemistry, and in particular to a technology for producing polyhaloid salts of organic compounds, in particular quaternary ammonium bases, and can be used to create effective bactericidal agents used to disinfect water and aqueous solutions.

Currently, generally accepted in the field of disinfecting aqueous solutions are methods associated with the addition of free oxidizing agents to the disinfected medium, for example, Cl ₂ , Br ₂ , I ₂ , O ₃ , etc. (Technical notes on water problems. - M .: Stroyizdat. - 1983.- T.1. - C.403-429). In this case, the disinfecting effect is expressed in the direct oxidation of microorganisms present in water or aqueous solutions, leading to their deactivation.

 The disadvantage of these methods is the toxicity of the products and the high cost of technological processes.

 A filler of a drinking water disinfection device is known, containing successively arranged layers of modified silver-containing cation exchange resin, solid iodine with particle sizes of at least 0.25 mm and a halide anion exchange resin, which is a highly basic anion exchange resin based on styrene-divinylbenzene copolymer (RF Patent 2043310, IPC C 02 F 1/50). Disinfection by this method is also due to the presence of free oxidizing agents.

 However, free oxidizing agents, along with microorganisms, oxidize many other substances present in the aquatic environment, making them toxic. So, for example, trihalomethanes are powerful carcinogens.

 More promising and safe are bactericides that work on the principle of "disinfection by signal." Such bactericides are complex polyhaloid derivatives of quaternary ammonium bases, which release the necessary portion of halogen when microorganisms appear in water or its solutions. The mechanism of their bactericidal action, other than that of free oxidizing agents, is not associated with the formation of harmful products due to the presence of iodine in a form that is able to participate only in addition reactions, but not oxidation. The most pronounced bactericidal properties of polygaloid compounds of Quaternary ammonium bases have polyiodide compounds.

Known bactericide for disinfection of water and the method of its preparation (US Patent 3923665, IPC C 02 B 3/06). The bactericide is a quaternary ammonium triiodide base of the general formula R ₄ N ⁺ I ₃ ^- , where R are organic radicals that can be of different nature, N ⁺ is a quaternary nitrogen atom carrying a positive charge, I ₃ ^- is a negatively charged polyiodide ion, which is a complex formation of iodide ion and one iodine molecule. A method of preparing a bactericide was to treat an ion-exchange resin based on Quaternary ammonium bases (PAO) with iodine dissolved in an aqueous solution of alkaline iodide.

 This invention provides compounds having bactericidal properties and representing quaternary ammonium bases - polyiodide ions, in which the iodine index has a value of not more than three. The bactericidal effect of PAO polyiodides on microorganisms in aqueous solutions is explained by the portioned release of iodine from polyiodides due to the partial neutralization of the positive charge of the nitrogen atom in PAO by microorganisms carrying a negative charge on their surface. However, these compositions have a relatively small bactericidal capacity.

Closest to the claimed is a method for producing disinfecting resins based on I ₅ - pentaiodide (US Patent 4999190, IPC A 61 L 2/16), which consists in treating an ion-exchange resin based on ChAO with iodine dissolved in an aqueous solution of alkaline iodide. In this case, an increase in the concentration of iodine in the solution is achieved by heating it to temperatures from the range of 30-60 ^o C.

This invention allows to increase the effectiveness of the bactericide due to the action of triiodide and molecular iodine adsorbed on the active centers of ChAO. However, the formation of pentaiodide ions (I ₅ ^- ) under the conditions proposed by this invention is problematic, since an excess of iodide ions in solution leads to exceptional formation of triiodide ions. An increase in the bactericidal efficacy of the composition obtained using the present invention is apparently due to the oxidizing ability of molecular iodine additionally adsorbed on the resin surface. Therefore, this composition has inherent disadvantages associated with the formation of toxic products as a result of direct oxidation of substances contained in water.

 The objective of the invention is to obtain polynodides Quaternary ammonium bases with improved bactericidal properties.

The problem is solved in that in a method for preparing a bactericide, comprising treating an ion-exchange resin based on a quaternary ammonium base with an iodine-containing solution, according to the invention, the solution is prepared by dissolving iodine in 0.1-0.4% alcohol alkali, and the treatment is carried out until a bactericide is obtained general formula
R ₄ NI _n • ((n-1) / 2) H ₂ O,
where n is an odd integer from 3 to 9,
R is an organic radical,
N is nitrogen
I - iodine.

In addition, to obtain a bactericide of the general formula R ₄ NI ₉ • 4H ₂ O, the resin is treated until the resin is completely saturated with iodine.

To obtain a bactericide of the general formula R ₄ NI _n • ((n-1) / 2) Н ₂ О, where n = 3, 5, 7, a solution of iodine in alcoholic alkali is prepared from stoichiometric calculation in the range of 0.5-1.2 g of iodine per 1 g of resin, and the resin is treated with a solution until the iodine is completely absorbed by the resin.

 After processing, the resin is washed with a concentrated solution of potassium iodide or sodium, then with deionized water until a negative reaction to free iodine is obtained, while the processing and washing are repeated.

In addition, the treatment of the resin with an iodine-containing solution is carried out at a temperature of 15-40 ^o C.

 Triiodide ion can form directly in solution with an excess of iodide ions. In this case, the triiodide ion is formed due to the linear electrostatic connection of two negatively charged iodine ions and one positive ion bound to one water molecule like a hydroxynium ion. Higher iodide ions, which have an index of iodine atoms of more than three, can form only after the binding of iodide ions to a positively charged PAO. The mechanism is essentially the same as in the formation of the triiodide ion. However, this mechanism assumes that the solution contains the smallest possible amount of iodide ion, which is not possible when PAO is treated with iodine from an alkaline iodide solution. The proposed method allows to obtain PAO polyiodides with an iodine content of more than three, since the treatment of PAO is carried out from an iodine-containing solution, the concentration of iodide ions in which is minimal.

 A method of preparing a bactericide is as follows.

It is known that in a solution of alcohol alkali a reversible equilibrium of the reaction is established:
R-OH + NaOH <--> R-ONa + H ₂ O,
where R is an organic alcohol radical.

Эти реакции также обратимы. Однако в присутствии четвертичного аммониевого основания в растворе, содержащем избыток йода (I₂), ионы [I^-Н₂ОI⁺]⁰ образуют нерастворимый комплекс с образующимся в этих условиях йодидом четвертичного аммониевого основания
R₄N⁺OH^- или R₄NCl^-+I^--->R₄N⁺I^- йодид,
R₄N⁺I^-+[I⁺H₂OI^-]⁰-->R₄N⁺[I^-H₂OI⁺]⁰I^- трийодид,
R₄N⁺[I^-H₂OI⁺]⁰I^-+[I^-H₂OI⁺]⁰-->R₄N⁺[I^-H₂OI⁺]₂ ⁰I^- пентайодид,
R₄N⁺[I^-H₂OI⁺]⁰ ₂I^-+[I^-H₂OI⁺]⁰-->R₄N⁺[I^-H₂OI⁺]₃ ⁰I^- гептайодид,
R₄N⁺[I^-H₂OI⁺]⁰ ₃I^-+[I^-H₂OI⁺]⁰-->R₄N⁺[I^-H₂OI⁺]₄ ⁰I^- нонайодид.The dissolution of iodine in alcohol alkali shifts the equilibrium to the right due to the involvement of water molecules in the process of hydrolysis of iodine, both in basic and in acid type

These reactions are also reversible. However, in the presence of a quaternary ammonium base in a solution containing an excess of iodine (I ₂ ), the [I ^- Н ₂ ОI ⁺ ] ⁰ ions form an insoluble complex with the quaternary ammonium base iodide formed under these conditions
R ₄ N ⁺ OH ^- or R ₄ NCl ^- + I ^- -> R ₄ N ⁺ I ^- iodide,
R ₄ N ⁺ I ^- + [I ⁺ H ₂ OI ^- ] ⁰ -> R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ⁰ I ^- triiodide,
R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ⁰ I ^- + [I ^- H ₂ OI ⁺ ] ⁰ -> R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ₂ ⁰ I ^- pentaiodide,
R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ⁰ ₂ I ^- + [I ^- H ₂ OI ⁺ ] ⁰ -> R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ₃ ⁰ I ^- heptaiodide,
R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ⁰ ₃ I ^- + [I ^- H ₂ OI ⁺ ] ⁰ -> R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ₄ ⁰ I ^- nonaiodide.

 The last compound is the highest member of the series, because the coordination number of nitrogen is four.

EFFECT: invention enables to obtain quaternary ammonium base polyiodides by treating the latter with iodine-containing solutions containing OH ^- ion and depleted iodide ions. Such solutions may be iodine solutions in alcohol alkali.

 The technological parameters of the process for the production of PAO polyiodides are presented in tables 1 and 2.

 The formation of individual compounds is impossible due to the partial temperature destruction of higher polyiodides with a decrease in the iodine index in the formula of compounds.

 Example 1

 To obtain a bactericide, anion exchange resin AB17-8 was taken, which is a quaternary ammonium base of styrene-divinylbenzene copolymers.

Resin in an amount of 100 ml (73 g) was placed in a reaction column. The reaction form of the resin had no effect on the further course of the processes, since during the first treatment with an iodine-containing solution, the resin was converted to the salt form (iodide). An iodine-containing solution was prepared in a separate container by dissolving crystalline iodine in a 0.1% alkali solution in 96% ethanol until saturated with iodine. The resin was treated with an iodine-containing solution at temperatures of 10, 15, 25, 30, 40, 50, 70 ^o With periodic passage of the iodine-containing solution through the resin layer in the column. A noticeable influence of temperature conditions in the range of 15-40 ^o C on the process was not detected. The iodine-containing solution was poured into the column, completely covering the surface of the resin, kept in contact with it for 10-15 minutes, then merged in the form of a clarified solution. After each treatment cycle, the resin was washed with deionized water until a negative reaction to free iodine was obtained (I ₂ ). The processing of the resin was repeated until it was completely saturated with iodine. An indicator of the complete saturation of the resin with iodine is the visual transparency of the solution being drained. The resin was washed with a concentrated solution of potassium iodide, then with deionized water until a negative reaction to free iodine was obtained, dried to obtain a constant weight, and the weight gain was determined. Based on the gain from stoichiometric ratios, taking into account the known exchange capacity of the resin, the formal composition of the obtained compound was calculated. Under the above conditions, a stoichiometric compound of R ₄ NI ₉ • 4H ₂ O or R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ₄ ⁰ I ^- was obtained by this method.

This formal composition is confirmed by experimental data on ion exchange in a saturated NaCl solution. After the exchange reactions, only iodide ions (I ^- ) were observed in the solution, and free iodine (I ₂ ) was not detected.

 Example 2

The bactericide was prepared by a method similar to that described in example 1. The difference was that the iodine-containing solution was prepared by dissolving crystalline iodine at a rate of 1.2 g of I ₂ per 1 g of resin in 4 liters of 0.4% alcohol alkali, and the resin was treated with the solution sequentially passing the entire volume of the solution through the resin until it is completely absorbed by iodine. Under these conditions, a bactericide of the composition R ₄ NI ₇ • 3H ₂ O or R ₄ N ⁺ [I ^- H ₂ OI ⁺ ] ₃ ⁰ I ^- was obtained.

 The mechanism of bactericidal action obtained in examples 1 and 2 of the compositions can be represented as follows.

In the interaction of the treated solution containing microorganisms with the bactericide obtained by the proposed method, iodine is released portionwise, but not in the form of an I ₂ molecule, but in the form of a pair of H ₂ OI ⁺ and I ^- ions. Ion H ₂ OI ⁺ kills microorganisms, while neutralizing their negative charge.

Evaluation of the bactericidal efficacy of the obtained compound was carried out on suspensions of E. coli cultures at various concentrations (10 ³ -10 ⁹ ). All experiments gave a positive result. After processing suspensions on bactericidal growth of colonies of microorganisms was not observed in any case.

Claims (5)

1. A method of preparing a bactericide, including the treatment of an ion-exchange resin based on a quaternary ammonium base with an iodine-containing solution, characterized in that the solution is prepared by dissolving iodine in 0.1-0.4% alcohol alkali, and the treatment is carried out to obtain a bactericide of the general formula:
R ₄ NI _n • (n-1) / 2 • H ₂ O,
where n is an odd integer from 3 to 9, R is an organic radical, N is nitrogen, I is iodine. 2. The method according to p. 1, characterized in that in order to obtain a bactericide of the general formula R ₄ NI ₉ • 4H ₂ O, the resin is treated until the resin is completely saturated with iodine. 3. The method according to p. 1, characterized in that to obtain a bactericide of the general formula R ₄ NI _n • (n-1) • Н ₂ О, where n = 3, 5, 7, a solution of iodine in alcohol alkali is prepared from stoichiometric calculation in the range of 0.5-1.2 g of iodine per 1 g of resin, and the resin is treated with a solution until the iodine is completely absorbed by the resin.  4. The method according to p. 1, characterized in that after processing the resin is washed with a concentrated solution of potassium iodide or sodium, then with deionized water until a negative reaction to free iodine is obtained, while the processing and washing are repeated. 5. The method according to p. 1, characterized in that the treatment of the resin with an iodine-containing solution is carried out at a temperature of 15-40 ^o C.

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