RU2137785C1 - Method of preparing disinfectant "ekosept" - Google Patents

Abstract

FIELD: household chemical goods. SUBSTANCE: method consists in two-step polycondensation of guanidine hydrochloride with diamine, in particular, diamine-ether or its mixture with alkyleneguanidine; first at 100-110 C and then at 140-150 C. Product can be used in medicine, veterinary, in waste water treatment, and in agriculture. EFFECT: increased antiseptic activity. 3 cl, 2 tbl, 9 ex

Description

 The invention relates to the field of chemical technology, in particular to the production of disinfectants, and can be used as an environmentally friendly disinfectant in medicine, veterinary medicine, in wastewater treatment and agriculture.

A known method of producing a disinfectant, including the interaction of hexamethylenediamine (HMDA) and a melt of guanidine hydrochloride (GHC) when heated. In this case, the HMDA is pre-melted and the process is carried out at a molar ratio of HMDA to GHC equal to 1: (0.85 - 0.95) with uniform addition of the obtained HMDA melt to the HH melt at 180 ^° C for 2.5 hours, followed by a temperature increase up to 240 ^o C and holding at this temperature for 5 hours (Aut. St. USSR N 1616898, class C 07 C 279/00, B.I. N48, 1990).

 The result is an antiseptic represented by polyhexamethylene guanidine salts.

 The disadvantages of this method include the toxicity of the process, because use a substance (HMDA) of hazard category I. In addition, the final product contains toxic impurities, has a low biocide, due to the non-optimal ratio of hydrophilic and hydrophobic fragments of the molecule.

 Closest to the proposed method is a method for producing a disinfectant by polycondensation of a guanidine salt with hexamethylene diamine (HMDA) by heating, followed by obtaining a salt of polyhexamethylene guanidine (PHMG). Water is added to the obtained PHMG salt to obtain a solution of 10-40% concentration, followed by the introduction of an equimolar amount of acid or its salt (RF Patent N 2052453, class C 07 C 279/02, B.I. N 2, 1996).

 The disadvantage of this method is the use of toxic GMA, which leads to a violation of the environmental friendliness of the process and contamination with toxic impurities of the final product. In addition, the guanidine salts used do not provide a disinfectant with sufficient biocide.

 The technical result achieved by this invention is to increase the antiseptic properties of the final product, significantly improve its environmental properties, significantly reduce the safety of the process.

To achieve a technical result in a method for producing a disinfectant by two-stage polycondensation of guanidine hydrochloride with diamine at elevated temperature, diamine is used as diamine or its mixture with alkylene diamine, polycondensation is carried out with an equimolar amount of guanidine hydrochloride and diamine ether, or a mixture of it with the first alkylene di the stage is 100 -110 ^o C, and in the second stage 140 - 150 ^o C.

 The invention is illustrated as follows.

Возможны также различные сочетания полиметиленовых радикалов в одной молекуле диаминоэфира в зависимости от способа его получения.Used industrially available diamines - substances of the General formula
H ₂ NR ¹ -OR ² -OR ³ NH ₂
H ₂ NR ¹ -OR ² -OR ³ -OR ⁴ NH ₂ ,
Where

Various combinations of polymethylene radicals in one diaminoether molecule are also possible depending on the method of its preparation.

 As alkylenediamines, for example, hexamethylenediamine (HMDA), deca- and dodecamethylene diamines are used.

 Diamino esters are used in the art to produce water-soluble polyamides. The raw material for their production is ethylene oxide or tetrahydrofuran. They have a number of significant advantages as components of polycondensation over α, ω-alkylenediamines.

 Firstly, they are an order of magnitude less toxic. Most diamino esters, especially the higher members of the series, are low toxic substances of hazard class IV.

 Secondly, unlike polymethylenediamines, diamino esters are non-volatile liquids that are easy to handle and do not sublimate from the polymerization mixture like HMDA.

 Finally, the presence of ether oxygen atoms in the molecule of diamino esters significantly increases their water solubility, makes polymers based on them more plastic. Thus, it is possible to obtain water-soluble antiseptics with optimal hydrophobicity by simple selection of the starting diaminoether.

The introduction of diamino esters into polycondensation with GH allows you to polycondensate their equimolar mixtures with GH without using special techniques. In this case, the polycondensation reaction proceeds smoothly at a temperature lower than for polymethylenediamines (100-150 ^o C) and leads for all of the listed diamino esters to an easily processed and water-soluble polyguanidino ester. The copolycondensation of GHC with mixtures of diamino esters and alkylenediamines also proceeds smoothly.

n=2-20; l=1,0; m=1,0; y=6,10,12;

X-Cl, анион неорганической или органической кислоты,
характеризуются пониженной токсичностью и высокими антисептическими свойствами.All synthesized polyoxyalkylene guanidines [ECOSEPT] of the general formula:

n is 2-20; l = 1.0; m is 1.0; y = 6.10.12;

X-Cl, an anion of an inorganic or organic acid,
characterized by reduced toxicity and high antiseptic properties.

 The treatment of aqueous solutions of polyoxyalkylene guanidine with alkalis results in the isolation of the corresponding bases, which, by the addition of suitable acids, can be converted into various salts of polyguanidino esters: phosphates, acetates, citrates, etc. The polycondensation temperature ranges are determined on the basis of experiments and are optimal. This is confirmed by the data in table. N 1.

Х = Cl^-).The method is illustrated by the following examples.
Example 1. To a sample of 4.7 g of GHC in a wide tube, 8 ml of 3,6-dioxaoctane-1,8-diamine are added. The test tube is placed in an oil bath. At a temperature of 100 ^o C begins the release of ammonia. The tube is kept at this temperature for 5 hours, then the temperature of the bath is increased to 140 ^o C and maintained at this temperature, periodically stirring by hand until the evolution of ammonia ceases (about 10 hours). At the end of the reaction, the product is cooled and analyzed. Determine the intrinsic viscosity in a 0.1 N NaCl solution, bactericidal activity against E. Coli (MPC,%), and toxicity in rats (LD ₅₀ mg / kg). Get polyoxyalkylene guanidine chloride - ECOSEPT.

X = Cl ^- ).

Х=Cl^-).Example 2. According to example 1, 4.7 g of GHC are condensed with 9 ml of 4,7-dioxadecane-1,10-diamine. The ECOSEPT polyoxyalkylene guanidine chloride is obtained. (

X = Cl ^- ).

Х=Cl^-)
Пример 4. К порции 5,3 г полидиоксододекангуанидина, полученной по примеру N 3, в 5 мл воды добавляют при перемешивании раствор 1 г NaOH в 2 мл воды. Отделяют нижний слой, представляющий собой основание от раствора NaCl, и нейтрализуют его добавлением орто-фосфорной кислоты до pH 7. Полученный раствор обезвоживают до постоянного веса. Получают фосфат полиоксиалкиленгуанидина "ЭКОСЕПТ" (Х= HPO $\genfrac{}{}{0ex}{}{\text{--}}{\text{4}}$ ).Example 3. By the method of example 1, 4.7 g of GHC are condensed with 10 ml of 4,9-dioxadodecane-1.12 diamine. The ECOSEPT polyoxyalkylene guanidine chloride is obtained. (

X = Cl ^- )
Example 4. To a portion of 5.3 g of polydioxododecanguanidine obtained in Example No. 3 in 5 ml of water, a solution of 1 g of NaOH in 2 ml of water is added with stirring. The bottom layer, which is the base, is separated from the NaCl solution and neutralized by the addition of phosphoric acid to pH 7. The resulting solution is dehydrated to constant weight. Get ECOSEPT polyoxyalkylene guanidine phosphate (X = HPO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ )

X=Cl^-).Example 5. By the method of example 1, 4.7 g of GHC are condensed with 11 ml of 4,7,10-trioxatridecan-1,13 diamine. The ECOSEPT polyoxyalkylene guanidine chloride is obtained. (

X = Cl ^- ).

X = Cl^-, y=6, m=0,5n)
Пример 8. По методике примера 7 сплавляют 10 г ГГХ, 8,7 ГМДА и 5,5 4,9-диоксадодекан - 1,12 - диамина. Получают сополимер оксиалкиленгуанидина "ЭКОСЕПТ" с хлоридом гексаметиленгуанидина". (

X = Cl^-, y=6, m=0,75n).Example 6. With a portion of 5.5 g of the polymer obtained according to example N5, the exchange decomposition is carried out according to example N4, and the obtained base is neutralized by adding citric acid to pH 7. The ECOSEPT polyoxyalkylene guanidine citrate is obtained (X = C ₈ H ₇ O $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ )
Example 7. In a 50 ml bottle under reflux, 10 g of GHC, 5.8 g of HMDA and 11 ml of 4,9-dioxadodecane-1,12-diamine are mixed. The flask is placed in an oil bath. At a temperature of 100 ^o C begins the release of ammonia. After an hour, the temperature of the bath was raised to 120 ^o C and maintained at this temperature for 5 hours, raised to a temperature of 150 ^o C and, periodically stirring, kept at this temperature for 10 hours. Receive a statistical copolymer of oxyalkylene guanidine "ECOSEPT'a with polyhexamethylene guanidine chloride." (

X = Cl ^- , y = 6, m = 0.5n)
Example 8. According to the method of example 7, 10 g of GHC, 8.7 HMDA and 5.5 of 4.9-dioxadodecane-1.12-diamine are fused. Get the copolymer of oxyalkylene guanidine "ECOSEPT" with hexamethylene guanidine chloride ". (

X = Cl ^- , y = 6, m = 0.75n).

X= Cl^-).Example 9. According to the method of example 7, 10 g of GHC, 2.9 HMDA and 5 of 1.12-dodecandiamine and 11 ml of 4,9-dioxadodecane-1,12-diamine are fused. Get ECOSEPT oxyalkylene guanidine terpolymer with hexamethylene guanidine chloride and dodecamethylene guanidine. "(

X = Cl ^- ).

 Table N 2 shows the properties of the antiseptic polyoxyalkylene guanidines "ECOSEPT".

Claims (3)

1. A method of producing a disinfectant by polycondensation of guanidine hydrochloride with a diamine by heating, characterized in that a diamine ester of the general formula is used as a diamine
N ₂ N - R ¹ - O - R ² - OR ³ - NH ₂ or N ₂ N - R ¹ - O - R ² - O - R ³ - OR ⁴ NH ₂ ,
Where

or a mixture thereof with an alkylenediamine selected from the group consisting of hexamethylene diamine, diaminodecane, diamindodecane, at equimolar ratios between guanidine hydrochloride and diamino ether or a mixture thereof with alkylene diamine, the polycondensation being carried out in the first stage at 100-110 ^° C, and in the second stage 140-150 ^o C.  2. The method according to claim 1, characterized in that after the cessation of ammonia evolution, alkali is added.  3. The method according to claim 1, or 2, characterized in that add inorganic or organic acid after the introduction of alkali and separation of a solution of sodium chloride.

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