RU2075381C1 - Antiseptic for protecting cellulose-containing materials - Google Patents

Abstract

FIELD: antiseptics. SUBSTANCE: invention relates to antiseptic compositions for biochemical protection of cellulose- containing materials against blue stain and yeast fungi and, in particular, for protection of wood and may be employed in lumber and woodworking industries. Composition contains following organic and inorganic components (in wt %): hydroxyethylidendiphosphonic acid, 10.0-12.0; alkylbenzylammonium chloride, 24.0-26.0; and sodium carbonate, 62.0-65.0. EFFECT: improved performance characteristics.

Description

 The invention relates to antiseptic preparations for the protection of cellulose-containing materials, in particular wood, against blue stain and mold during its atmospheric drying and transportation with humidity higher than transport and can be used in sawmilling and woodworking industries.

 Known antiseptic preparation for protecting wood from fungi blue stain and mold, containing, in wt. sodium pentachlorophenolate 36.5, transformer or spindle oil 2.0, ethyl mercurchloride 0.48, sodium hydroxide 0.5, soda ash remaining (see Flomin E.E. et al. Protective processing of raw lumber, M. 1970. p. 4 and 9).

 The drug is not able to quickly stop the development of microorganisms. It has an unpleasant annoying odor. The active basis of the drug is sodium pentachlorophenolate, which weakly penetrates into the wood and thereby reduces the effectiveness of the drug to protect wood from decay. The use of this antiseptic is complicated and limited by the fact that it acts selectively on microorganisms.

 Known antiseptic composition for protecting raw wood and lumber from rotting, containing, in wt. sodium pentachlorophenolate - 38.0-42.0, thiourea 10.0-12.0, mineral oil 2.0-2.5, triphenylphosphate 1.5-2.0 and sodium carbonate -41.5-48.5 ( see author's certificate of the USSR N 489638, class 4 B 27 K 3/52 dated 3.12.73).

 The disadvantage of this antiseptic is that its activity is manifested only at high concentrations of working solutions. Antiseptic belongs to the 1st class of danger; It is toxic to humans and the environment. The effect of the antiseptic is manifested with the constant replenishment of working solutions, and at the same time, the quality of wood decreases sharply and its processing technology deteriorates.

 The closest in technical essence is an antiseptic composition for protecting wood from blue stain and mold fungi, containing, in wt. soda ash -57.5 ± 1, trisodium phosphate 13.0 ±, boric acid -5.5 ± 0.5 and alkyldimethylbenzylammonium chloride -24.0 ± 1. This product is commercially available under the name "KATAN" (see Specifications TU OP 13-1273675-29-90, developed by VNPO Soyuznauchdrevprom, 1990).

The disadvantage of this tool, selected by the applicants as a prototype, is its high level of toxicity. This is due to the fact that the active basis of the drug is alkyldimethylbenzylammonium chloride. The specified compound has a skin-irritating and pronounced skin-resorptive effect, causing dermatitis. The drug requires control during dosing and preparation of working solutions. In addition, its antiseptic properties are mainly manifested when its concentration in solutions is from 5 to 8%, and for spruce wood, the concentration of solutions should be 5-7% and for pine wood 6-8%. The compound alkyldimethylbenzylammonium chloride belongs to hazard class 2. The safe level of exposure to the compound is 0.07 mg per 1 m ³ , and the MPC in water of water bodies is 0.1 mg per 1 liter.

The working solution of the drug have a pH = 8.8-9.5. The average consumption of antiseptics is 1.75 kg per 1 m ^{3 of} wood. The index of surface safety of samples of coniferous and deciduous species of sapwood against wood-staining and mold fungi at a 5% concentration of the working solution is 88% after exposure for 30 days and 73% after exposure for 50 days. When the concentration of the working solution of antiseptic 6 and 8%, the safety index of images after 30 days of exposure is 94% and after 50 days - 90-91%
All of the above disadvantages of the prototype are eliminated if you use the composition of the antiseptic according to this invention. This antiseptic contains soda ash, a quaternary ammonium compound, which is used as alkylbenzylammonium chloride, and additionally hydroxyethylidene diphosphonic acid, with all components taken in the following ratio, in wt.

soda ash 62.0-65.0
alkylbenzylammonium chloride 24.0-26.0
hydroxyethylidene diphosphonic acid 10.0-12.0.

 Thus, the common features of the proposed antiseptic and prototype are the presence of soda ash and a quaternary ammonium compound in it, and the distinguishing feature is that it contains an additional component in the form of hydroxyethylidene diphosphonic acid and that alkylbenzylammonium chloride is used as a quaternary ammonium compound.

 Soda ash (sodium carbonate) is a white powder, soluble in water and insoluble in most organic solvents. This compound is used in the pharmaceutical industry, leather, rubber and food. In addition, soda is used for the production of glass, aluminum, detergents, oil refining, washing and washing materials.

БИОМИН хорошо растворим в воде и представляет собой однородную массу в виде пасты с содержанием основного вещества не менее 48-50% Плотность раствора, г/см³ 0,96-0,97, pH 6,6-7,0, вязкость при 20^o, спз - 140-150, поверхностное натяжение, дин/см 32-35 и токсичность для белых мышей LD₅₀, мг/кг 350. Соединение относится к 3 классу опасности. БИОМИН обладает бактерицидными свойствами и применяется он в качестве эмульгатора и дезэмульгатора.Alkylbenzylammonium chloride is a surfactant. In industry, it is produced under the name "BIOMIN". The compound has the structural formula:

BIOMIN is soluble in water and is a homogeneous paste in the form of a paste with a basic substance content of at least 48-50%. Density of the solution, g / cm ³ 0.96-0.97, pH 6.6-7.0, viscosity at 20 ^o , SPR - 140-150, surface tension, dyne / cm 32-35 and toxicity for white mice LD ₅₀ , mg / kg 350. The compound belongs to hazard class 3. BIOMIN has bactericidal properties and is used as an emulsifier and demulsifier.

Oxyethylidene diphosphonic acid is a strong pentaic acid. It is used in the oil industry, in agriculture, in the perfumery and cosmetics industries, in household and analytical chemicals, and in the power system as an anti-scale agent. Oxyethylidene diphosphonic acid (OEDPK) is a surfactant and is also used as a disinfectant, water repellent, corrosion inhibitor, demulsifier and bactericide. Due to its low bioprotective properties, it is practically not used as a bactericide in industry. The MPC of this compound in drinking water bodies is 0.6 mg / dm ³ , and for fisheries 0.9 mg / dm ³ . OEDFK belongs to the 3rd class of danger. To obtain the proposed composition, the antiseptic OEDFK must comply with GOST 12.1.007-76.

Each component in the proposed antiseptic performs its function. So soda ash accelerates the transfer of the active part of the mixture, which includes alkylbenzylammonium chloride and hydroxyethylidene diphosphonic acid. Oxyethylidene diphosphonic acid activates the vital activity of the fungal flora of wood, lowering its resistance to fungicides. In the mixture, the effect of HEDPA is much higher than that of similar compounds, for example, trisodium phosphate, because the phosphorus content in it is almost two times higher. Alkylbenzylammonium chloride, as the active biological part of the mixture, destroys the fungal flora of wood. This compound is in the composition in the form of a complex containing a hydroxyl group, which is the dominant element in terms of bactericidal and fungicidal activity of the proposed composition. The replacement of halogen Cl ^- with a hydroxyl group occurs in aqueous media. The drug exhibits its antiseptic properties at a concentration of 5-7% in aqueous media
Thus, each of the used antiseptic components performs its specific function of bioprotection and at the same time enhances the effect on each other, increasing the effectiveness of the antiseptic. In this case, the toxicity of the drug is significantly higher than the toxicity of two components, in particular BIOMINA and OEDFK.

All components of the proposed antiseptic are moderate substances in their chemical activity. Antiseptic belongs to the 3rd class of danger. It is safe for humans and the environment, while working with it, the usual means and protective measures are recommended, which are recommended when working with chemicals. In industry, the proposed antiseptic is called "BIOMINAS-2." Get it by mixing all three components. For this, BIOMIN and OEDFK are mixed beforehand in a special mixer at 50 ^o C, the mixture is thoroughly mixed for several hours (up to 2 hours, depending on the volume of incoming substances) and this mixture is fed into another mixer, which is also equipped with a special mixer and heating. First, sodium carbonate is introduced into this mixer, it is thoroughly mixed and a mixture of BIOMIN and OEDFK is introduced through the nozzles (by the method of periodic pollination of the mixture).

The resulting mixture is stirred at a temperature of 50 ^o C and when it contains a mass fraction of carbonates in terms of CO $\genfrac{}{}{0ex}{}{\text{-2}}{\text{3}}$ at least 23%, it is unloaded and sent for sale.

The finished product is a homogeneous powdery mass of white, almost odorless. The antiseptic is completely soluble in water, pH 8.8 9.5. The melting point is 198 199 ^o C, the freezing temperature is -25 ^o C, the density of g / cm ³ , 1.25. The maximum concentration limit in water of reservoirs is 1.8 mg / m ³ , and according to the prototype -0.1 mg / l, the safety level in the air is 0.037 mg / m ³ , and according to the prototype -0.07 mg / m ³ .

The quality of the antiseptic is judged by the surface preservation of wood samples previously infected with a spore suspension (wood-staining and mold fungi) and dried to their original moisture. The average consumption of BIOMINAS-2 is about 570 680 g / m ³ , while the prototype is 1.75 kg / m ³ , which is an additional advantage over the prototype. It was found that the antiseptic effect has the greatest toxicity effect at a 5-7% concentration, and the bioprotective properties of the drug are most found for samples infected with wood-coloring fungi, and less for mold fungi. So at 5% concentration after 30 days of exposure, the safety of the samples is 87% -88% as in the prototype, and at 7% after 30 days it is already 95%, while in the prototype 94% safety is achieved only at 8% th concentration of the working solution. At 8% concentration of BIOMINAS-2 after 30 days, the safety is 96%. The technical effect is increased due to the fact that the proposed antiseptic is less dangerous for the environment and that its consumption is much less than that of the prototype.

 Examples of specific performance.

Example 1. In a special mixer equipped with heating and a stirrer, alkylbenzylammonium chloride and hydroxyethylidene diphosphonic acid are introduced. The content of these components in wt. is 25 and 11 respectively. At a temperature of 50 ^o C the mixture is thoroughly mixed for 1.5 to 2 hours and served in an intermediate tank, from where the mixture through nozzles enters another mixer filled with sodium carbonate. The latter is taken in quantity, wt. equal to 64. A mixture of BIOMIN and OEDFK is introduced into soda ash by spraying, and periodic. As a result, each particle of sodium carbonate is "enveloped" in a liquid mixture, contributing to the formation of such a mixture of components, which quickly dissolves in water with the formation of an antiseptic solution. After thoroughly mixing the mixture, the carbonate content is determined in it, which should be calculated in terms of CO $\genfrac{}{}{0ex}{}{\text{-2}}{\text{3}}$ not less than 23% Ready antiseptics are packaged and sent for sale.

 The antiseptic properties of the resulting product are expressed in terms of the preservation of wood samples previously impregnated (infected) with a spore suspension and dried to their original moisture content. As a result, the preservation rate of samples at 5% concentration of the drug after 30 days is 89% and at 7% 95% and 8% 96%. For samples impregnated with molds, the protection efficiency is less.

As a result of determining the safety index of the samples after 10, 20 days, it was revealed that at 5% concentration this indicator was 97 and 91%, respectively, and at 7% 99 and 96%, respectively. Under the same conditions, the surface preservation indices of the samples after 10 days according to the prototype were 88% at 5% concentration and after 20 days 88% at 7% concentration, these indicators are respectively 97 and 95%
Example 2. BIOMIN and OEDFK, wt. 26.0 and 12.0. The mixture is thoroughly mixed at 50 ^o C and injected through nozzles into another mixer with a mixer where sodium carbonate is present in an amount of 62.0 wt. All technological conditions are similar to example 1, with the only difference being that the components are introduced in a different amount. A white powder is obtained, finely dispersed and highly soluble in water. The pH of the medium was 8.8–9.5; the antiseptic properties were checked, as in Example 1. As a result, at 5% concentration of BIOMINAS-2 antiseptic, the safety of samples after 30 days was 88% and at 7%, 94%
Example 3. Analogously to example 1, with the only difference being that the components in the composition are taken in quantities, wt. BIOMINA 24.0, OEDFK 11.0 and soda 65. The safety of samples after 30 days at 5% concentration was 87% and at 7% 94.5%
It was determined that the greatest effect on the protection of wood is achieved when using an antiseptic, when the components are taken within the limits specified in the formula, with quantitative indicators less and more than the specified limits, the antiseptic activity of the drug decreases.

 The proposed antiseptic expands the range of well-known combined preparations for bioprotection of wood from decay and is considered one of the promising means for protecting wood from damage from its wood-coloring mushrooms.

Claims (1)

 An antiseptic for the protection of cellulose-containing materials containing soda ash and a quaternary ammonium compound, characterized in that it contains alkylbenzylammonium chloride and optionally hydroxyethylidene diphosphonic acid as a quaternary ammonium compound in the following ratio of components, wt. Soda ash 62.0 65.0
Alkylbenzylammonium chloride 24.0 26.0
Oxyethylidene diphosphonic acid $ 10.0 12.0