WO2008108680A1

WO2008108680A1 - Method for long acting disinfection of areas and facilities and for conservation and decontamination of water.

Info

Publication number: WO2008108680A1
Application number: PCT/RU2007/000617
Authority: WO
Inventors: Olga Nikolaevna Skorokhodova; Irina Ivanovna Vointseva; Igor Viktorovich Kazennov; Olga Markovna Kazakova; Oleg Narevich Dobrokhotsky; Tatyana Khalitovna Borzenkova; Roman Vladimirovich Borovik
Original assignee: Obschestvo S Ogranichennoi Otvetstvennostyu 'evima-M'
Priority date: 2007-03-07
Filing date: 2007-11-12
Publication date: 2008-09-12
Also published as: RU2329286C1

Abstract

The inventive method for producing coatings which exhibit disinfecting properties used for sanitising areas and facilities and for conserving and decontaminating water, including potable water, consists in producing polyhexamethylene guanidine derivative in the form of a base or an organically soluble in the form of oleate, pelargonate, undecylenate from polyhexamethylene guanidine chloride, in mixing the solution of said derivative in water or in an organic solvent with the solution of a hydrophobic film-forming polymer, selected from a range of chlorosulfonated polyethylene and polythrichlorobutadiene, in an organic solvent in such a way that a film-forming interpolymer is formed, is applied to a previously prepared surface in the form of a coating consisting of at least three layers, possibly in the form of a composition, and is finally hardened, with proviso that the ratio between the polyhexamethylene guanidine derivative and the hydrophobic polymer ranges from 7.5-45.0 parts by weight and 55.0-92.5 parts by weight, respectively. The other variant of the method consists in applying a coating made of epoxy resin combined with a polyhexamethylene guanidine base to a previously prepared surface. After hardening, the ratio between said agents ranges from 32-34 parts by weight and 66-68 parts by weight, respectively.

Description

METHOD OF LONG-TERM DISINFECTION OF PREMISES, EQUIPMENT, CONSERVATION AND DISINFECTION OF WATER

DESCRIPTION OF THE INVENTION

The invention relates to polymer chemistry, namely, to obtain a disinfectant based on interpolymers of polyhexamethylene guanidine and film-forming polymers, which can be used for prolonged disinfection of rooms with a large crowd of people under conditions of increased epidemiological danger (including tuberculosis); for protection against biological destruction by various types of mushrooms of wooden structures; for protection against biofouling of equipment surfaces in contact with water (including drinking); for preservation and disinfection of drinking water.

State of the art

Currently, the world is abandoning the use of traditional disinfectants based on chlorine-containing compounds because of their toxicity, volatility, instability and corrosion activity. The disadvantages of these compounds is also the relatively short duration of the antimicrobial effect, limited to only a few hours, after which the preparations disappear and surface treatment has to be repeated, however, due to their high toxicity and allergenicity, room processing cannot be carried out in the presence of people.

Similarly, chlorine quickly evaporates from water; after which highly toxic organochlorine compounds remain in the water, which chlorine forms with the impurities contained in the water. Chlorine-containing compounds are increasingly being replaced by less toxic and more stable biocidal preparations, in particular high-molecular compounds containing guanidine groups - polyguanidines in the macromolecule. Known bactericidal agent polyhexamethylene guanidine (PHMG) [SU 247463, 1968, class. A 61 L], which is a polymer with a molecular weight of ~ 10000 and a repeating unit formula:

[~ (CH ₂ ) ₆ - NH-C-NH-J _n ,

Il

NH ₂ ⁺ A ^" where A ^" is OH ^" or an acid residue of an organic or inorganic acid; n = 50-60.

PHMG is a solid, readily soluble in water; not soluble in organic solvents. Aqueous solutions are colorless and odorless, stable during storage, do not cause corrosion of equipment, discoloration of tissues, allergies in humans.

Derivatives of PHMG possess a wide spectrum of antimicrobial activity in air and water: effective against gram-negative and gram-positive bacteria (including tuberculosis mycobacteria), simultaneously affect aerobic and anaerobic microflora; viruses, dermatophytes, mold, yeast-like wood-destroying and wood-staining fungi; in the aquatic environment they effectively suppress unwanted microflora and algae. The biocidal properties of PHMG derivatives are due to the presence of guanidine moieties in the repeating units of their macromolecules.

In relation to warm-blooded (human and animal) PHMG has low toxicity: in terms of acute toxicity, the drug belongs to class III of moderately hazardous substances when introduced into the stomach, to class IV of low-hazard substances when applied to the skin (according to GOST 12.1.007).

In practice, not the very high molecular weight PHMG base is usually used, but its hydrophilic salts with mineral or organic acids, which are more stable substances. Their dilute aqueous solutions are used as biocidal additives in water (drinking, swimming pools, wastewater) and water-borne compositions (whitewash, water-based paints and varnishes, cement).

It is known to use PGMG chloride as a disinfectant [SU 1616898, 12.30.1990], which is intended for the disinfection of surfaces in medical facilities, in medical and preventive institutions, in children's facilities, in public facilities, catering establishments, and in everyday life. For disinfection, 0.5-4.0% aqueous polymer solutions are used. After drying, the polymer forms a thin biocide film on the surface, which retains antimicrobial activity for 7 days, after which the surface treatment with the polymer solution is repeated [Methodological instructions for the use of the disinfectant Biopag-D Na 11-3 / 489-09, M., 2002].

The disadvantages of the known disinfectant are the relatively short duration of its antimicrobial action, stickiness and lack of mechanical strength of the biocidal coating, which is also easily washed off with water.

It is known to use PGMG chloride for biocidal water treatment of circulating industrial water supply systems for industrial enterprises [SU 1773876, 11/07/1992]. However, this method of biocidal water treatment requires constant monitoring and maintaining the concentration of PHMG in water. In addition, the method is not suitable for the treatment of drinking water, since the minimum inhibitory concentration of PHMG for E. coli is 0.5-2.0 mg / l, for green and blue-green algae - 2.0 and 37.5 mg / l, respectively while the maximum permissible concentration of PHMG in drinking water is 1.0 mg / l.

It is known the introduction of PHMG in the form of a base or a water-soluble salt as a bactericidal additive in paints and varnishes [RU 213 18 97, 20.06.1999]. However, hydrophilic derivatives of PHMG are poor It is combined with a hydrophobic film-forming base of paints and varnishes. In addition, biocidal paints obtained by simple mixing of the components without chemical interaction between them do not have the necessary water resistance: in aqueous media or under the influence of atmospheric precipitation, PHMG leaches from the coating, which quickly loses its biocidal properties.

Various crosslinked polymer compositions are known for waterproof coatings of bactericidal action, in which the PHMG is chemically bonded to chemically complementary hydrophobic film-forming polymers.

So from [SU 172 82 64, 23.04, 1992] known polymer composition, which contains 35-65 parts by weight poly-l, l, 2-trichlorobutadiene or poly-1,2,3-trichlorobutadiene and 65-35 parts by weight foundations of PHMG. A 2% aqueous solution of PHMG base is mixed with a 2% solution of polytrichlorobutadiene in chloroform in the presence of a 0.1 N sodium hydroxide solution until alkaline according to the universal indicator. The lower layer is separated, washed with distilled water, dried over calcium chloride at room temperature. The solution is filtered off from calcium chloride, evaporated twice, sprayed onto a defatted surface, dried at 40 ⁰ C. Coating characteristic: the coating does not peel off from the surface for 2 months when exposed to water at 25 ⁰ C; removal of microbial bodies in 40 minutes of contact - 99.9%; peeling resistance - 19.2 n / cm ² , breaking tensile stress - 16 MPa. The disadvantage of this known composition is the relatively short duration of the protective effect (2 months), in addition, it does not have a stable bactericidal activity (in real conditions of use, complete inactivation of test microorganisms is not achieved and after 3 days their reactivation is observed).

From [RU 205 58 44, 03/10/1996] a bactericidal coating composition is known containing an organic binder based on film-forming polymers and bactericidal polymer - base or chloride PGMG.

As an organic binder, chlorine-containing polyethylene or epoxy resin is used in the following ratio of components, parts by weight:

Derivatives of PGMG - 10-75

Chlorine-containing polyethylene - 90-25

The composition is prepared by mixing the components in bulk or in solution, applied to the protected surface with a brush, pneumatic spray or in bulk, dried at 20-120 ⁰ C.

This patent does not define methods for producing biocidal coatings (number of layers, coating thickness, curing conditions), which provide the necessary mechanical strength and prolonged disinfecting effect of coatings in air and aqueous media. Meanwhile, the application of the compositions in one layer is not always sufficient to ensure a stable bactericidal effect of coatings; curing of epoxy compositions at a temperature of 20-120 ⁰ C does not lead to 100% crosslinking of the reacting polymers, and free PHMG is present in the water above the coating in an amount exceeding the maximum permissible concentration.

From RU 218 17 37.04.04.2002 a bactericidal coating composition is known, which includes an organically soluble paint or varnish and a bactericidal component, which are used as derivatives of PHMG with a ratio of components, parts by weight:

Derivative of PGMG - 0.35-9.00

Organically soluble paint or varnish - 91, 00-99.65

As organosoluble paints or varnishes, varnishes based on chlorosulfonated polyethylene, for example, XCPE-188, XSPPE-7120, pentaphthalic paints, for example, PF-1 15, PF-218PG, are used, nitrocellulose varnishes, for example, grades НЦ-132П, НЦ-11, НЦ-11A, НЦ-132K, НЦ-262, НЦ-222, НЦ-243, НЦ-589, or oil paints, for example, grades MA-15H, MA -22H, MA-21, MA-25, etc.

The derivatives of PHMG use its base, chloride, fluoride, phosphate, stearate, sorbate, carboxyl cellulose, isophthalate, acetate, oleate, folate, oxalate and dehydroacetate in the form of a concentrate of a 0.3-30% aqueous emulsion solution. According to the description of the invention, the bactericidal composition is prepared by mixing concentrates of derivatives of PHMG with concentrates of paints or varnishes with further dissolving the mixture in an organic solvent or introducing the bactericidal paste in the usual way into the finished paint or varnish at room temperature before use. The finished bactericidal composition is applied to the surface of products made of metals, ceramics, concrete, brick, wood and other materials with a brush, roller, spray or watering, then dried at 20-120 ⁰ C.

However, aqueous solutions cannot be prepared from fluoride, oleate, sorbate, stearate, PHMG dehydroacetate, since these salts are not soluble in water [RU 205 24 53, 01.20.1996]. Aqueous solutions of the remaining mentioned derivatives of PHMG are not compatible with organo-soluble hydrophobic polymers, which are the film-forming base of paints and varnishes. From RU 223 64 28, 09/20/2004 a composition is known for a coating that disinfects indoor air and protects materials from biodeterioration, including chlorosulfonated polyethylene, an organic solvent, water, PHMG and dialkylphosphoric acid in the following ratio of components, May. h:

Chlorosulfonated Polyethylene 9.7-14.1

PHMG 0.6-3.1

Dialkylphosphoric acid 2.0-7.3

Water 0.3-12.2

Organic solvent rest In this case, PHMG forms organosoluble compositions with chlorosulfonated polyethylene in the presence of dialkylphosphoric acids. To obtain such compositions, an aqueous solution of the PHMG salt, for example, chloride, is treated with alkali, the polymer layer of the PHMG base is separated and treated with a solution of chlorosulfonated polyethylene in an organic solvent with the addition of dialkylphosphoric acid.

However, with the specified composition, the dry residue of varnish is 10.3-17.2%. It is known that at such a high concentration of reaction between the polymers are always accompanied by the formation of crosslinked interpolymers [II. Vointseva. Irreversible interpolymer reactions in solution. Dis. Doctor of Chemistry, IVS RAS, St. Petersburg, 1992], therefore, the viability of such a composition is small and it quickly and irreversibly loses fluidity. In addition, it does not follow from the description that the coating provides a prolonged disinfecting effect.

From RU 225 41 44, 20.06.2005, another interpolymer disinfectant is known including a polyguanidine base, a chlorine-containing polymer, an aromatic solvent and ethyl alcohol. As the base of polyguanidine, a polyalkylene guanidine base or a polyoxyalkylene guanidine base or a polyalkylene biguanide base is used; as a chlorine-containing polymer, a mixture of chlorosulfonated polyethylene with chlorinated polyvinyl chloride in a ratio of 7.3-10.1: 1 is used; as aromatic solvent used nefras in the following ratio, May. h. The base of polyalkylene guanidine, or the base of polyoxyalkylene guanidine, or the base of polyalkylene biguanide 0.3-0.5

A mixture of chlorosulfonated polyethylene with chlorinated polyvinyl chloride in the ratio of 7.3: 10.1: 1 3.1 -4.0

Ethyl alcohol 7-10

Nefras rest

The patent also does not describe methods for producing biocidal coatings (number of layers, coating thickness, curing conditions), which provide the necessary mechanical strength and prolonged disinfecting effect of coatings in air and aqueous media.

RU 213 32 56, 07/20/1999 describe the Ekotermofoc bactericidal paint, including a binder, titanium dioxide and a bactericidal additive. The paint contains alumina-phosphate binder, and as a bactericidal additive - PHMG phosphate and additionally magnesium oxide, silicon dioxide, aluminum hydroxide and calcium carbonate in the following ratio of components, parts by weight:

Titanium dioxide 9.0-31, 4

Phosphate PGMG 3.0-7.0

Magnesium Oxide 0.4-2.3

Silica 1.6-4.8

Aluminum hydroxide 0, 1 - 1, 0

Calcium carbonate 0.3-3.1

Alumoborophosphate binder the rest

The technical result is an increase in the antimicrobial properties of the paint, its adhesive characteristics and water resistance.

RU 214 24 51, 12/10/1999 describes the preparation of an antiseptic agent - PHMG phosphate, which can be used in medicine, veterinary medicine and agriculture. A method for producing an antiseptic phosphate of PHMG is described, including the operation of exchange decomposition of a salt of PHMG with a phosphorus-containing component by heating, subsequent washing and drying of the target product. As a salt of PHMG a 50% aqueous solution of PHMG chloride is used, and a 40% aqueous solution of disubstituted ammonium phosphate is used as the phosphorus-containing component, while the ratio of the solution of PHMG chloride to the solution of disubstituted ammonium phosphate is in the range (2-2.5): 1. The technical result is an increase in the antiseptic properties of the final product, as well as a simplification of the process technology.

RU 216 9163, 06/20/2001, describes a biocidal paint composition that includes chlorine-containing polyethylene, a base of PHMG and a solvent, additionally contains active pigment and carboxylic acid, and as a solvent the composition contains ethyl alcohol and toluene in the following ratio, wt.h. : Chlorinated polyethylene 2.8-3.0

Base PGMG 0.4-0.5

Active pigment 3.5-9.0

Carboxylic acid 0.05-0.1

Ethyl alcohol 4,5-55

Toluene rest.

EFFECT: increased water resistance of a coating, improved strength characteristics and decorative appearance of coatings based on a biocidal paint composition.

Paint and varnish compositions can be used to protect surfaces operating in the air, for example, for treating walls in rooms with high humidity or with a large crowd of people under conditions of increased epidemiological danger (including tuberculosis). The biocidal effect of the coating lasts at least 6 months (observation period).

The inventive paint composition can be applied to surfaces operated in an aqueous environment, for example, the inner surfaces of containers for storing drinking water, pipelines. A water-borne composition for bactericidal coatings of ceramics, concrete, brick, plaster and other materials in the air is also known from RU 218 9999, 09/27/2002, including water-borne paint and a bactericidal component - derivatives of PHMG. Moreover, the water-borne composition contains as a bactericidal component derivatives of PHMG (base, chloride or phosphate) in the following ratio of components, parts by weight:

Derivative of PHMG 0.5-9.0

Waterborne paint 91-99.5

EFFECT: creation of a coating with stable bactericidal properties, which has a wide range of biocidal properties and is safe for humans.

A biocidal epoxy coating composition is known from RU 228 2649, 08.27.2006, including TAHEP-5341 or TAHEP-622 organosoluble epoxy enamel, PHMG chloride as a bactericidal component, and fungicide - hexcaridpo-l, 3,5-tris (hydroxyethyl) trazine , while the mass ratio of hexahydro-l, 3,5-tri- (hydroxyethyl) thiazine and PHMG chloride is 1: 1, with the following ratio of components, parts by weight:

The above organosoluble enamel 100

PGMG chloride 1.5-3.0

Hexahydro-1, 3,5-tri- (hydroxyethyl) thiazine 1,5-3,0

As the well-known level regarding the production of disinfectants, biocidal protection of various surfaces shows, PHMG and its derivatives are widely used for these purposes, however, the increased requirements for such agents still require improvement of these agents, increasing their antiseptic ability.

Therefore, the technical task of the claimed invention is a further improvement in the creation of disinfectants, as for disinfecting water, preserving it, and in the form of disinfecting coatings.

SUMMARY OF THE INVENTION

So, the technical task of the claimed invention is a further improvement in the production of disinfecting coatings with a prolonged biocidal action for the treatment of premises, equipment, as well as the preservation and disinfection of water.

The stated technical problem is achieved by the claimed group of inventions, which is a variant of the method for prolonged disinfection of premises, equipment, preservation and disinfection of water. This task is achieved by the preparation of interpolymer compositions of the optimal qualitative and quantitative composition under conditions that ensure the maximum viability of the composition, as well as the layer thickness and the curing mode of the interpolymer compositions, providing water-resistant coatings.

So, the technical task is achieved by the method of prolonged disinfection of premises, equipment, preservation and disinfection of water, including: a) obtaining a derivative of PHMG in the form of a base or organically soluble salt in the form of oleate, pellargonate, undecylenate from PHMG chloride; b) preparing a solution of the specified in (a) derivative of PHMG in water or an organic solvent; c) preparing a solution of a hydrophobic film-forming polymer selected from the group consisting of chlorosulfonated polyethylene, polytrichlorobutadiene in an organic solvent; g) the formation of an interpolymer disinfectant composition in combination with mixing conditions of 0.3-2.9 wt.h. 3.6-9.0% of a solution of the derivative of PHMG and 2.3-3.7 wt.h. 3.2-5.0% solution of the specified hydrophobic polymer; d) applying to the previously prepared coating surface of an interpolymer disinfectant composition from step g), if necessary, in the form of a composition containing target additives; 5–20 µm thick non-pigmented coating, possibly in several layers; f) each coating layer is dried first at ambient temperature, and subsequent final curing is carried out at a temperature of 50-80 ⁰ C, while the ratio between the PHMG derivative and the hydrophobic polymer in the cured interpolymer (coating) is 7.5–45.0, respectively parts by weight and 92.5 - 55.0 parts by weight

The technical problem is also achieved by another variant of the method of prolonged disinfection of premises, equipment, preservation and disinfection of water, including: a) obtaining the basis of PGMG from chloride PGMG; b) the formation of an interpolymer disinfectant composition when combined under conditions of mixing 10 to 35 wt.h. the basis of PHMG from stage a) in the form of a 15-23% solution in water or without solvent, from 20 to 65 parts by weight epoxy resin in the form of a 60% dispersion in water or without solvent, if necessary in combination with a hardener for it; c) applying to a previously prepared surface an interpolymer disinfectant composition, possibly in the form of a composition containing target additives, with a thickness of 15-120 microns; g) subsequent curing of the coating at 130-150 ⁰ C and the ratio between the derivatives of PHMG and epoxy resin is in the range of 32-34 parts by weight, respectively. and 66-68 parts by weight

The technical problem is achieved by the fact that a disinfecting composition is applied to the prepared surface of the room or equipment, containing an interpolymer obtained from the base or the indicated organosoluble salt of PHMG and a chemically complementary film-forming polymer; polymer coating is cured. When the expected contact of the cured coating with drinking water from the coating is extracted chemically unbound (free) PHMG.

PHMG chloride is used as a feedstock to obtain a biocidal component of the compositions. This polymer does not combine with organically soluble film-forming polymers, as it does not dissolve in any organic solvent. The PHMG chloride is treated with alkali to obtain the PHMG base soluble in lower alcohols. When the PHMG base is treated with oleic, pellargonic or undecylenic acid, the salt of PHMG soluble in aromatic solvents (oleate, pellargonate, undecylenate) is obtained.

The following examples illustrate the invention, but do not limit it. Specific curing conditions and coating thicknesses for Examples 1–5 are indicated in the corresponding Examples 1.1–5.2.

DETAILED DESCRIPTION OF THE INVENTION Disclosure of the invention. Composition JVsI. Composition based on chlorosulfonated polyethylene (HSPE) and PHMG base.

The composition is intended to protect equipment operated in contact with water (drinking and technical purposes), to protect wood, as well as for prolonged disinfection of premises. Reacting polymers do not have a common solvent, so the composition is prepared in a mixture of two solvents: ethyl alcohol and an aromatic solvent.

The composition contains 0.3-0.8 parts by weight of PHMG base in the form of an 8-9% solution in ethanol and 3.2-3.7 parts by weight of ChSPE in the form of a 3.2 - 3.3% solution in an aromatic solvent.

The hydrophobic film-forming polymer - KhSPE has an MM of ~ 20,000 conventional units. and the structure of the repeating unit: ~ (CH ₂ -CH -) -.

SO ₂ Cl As an aromatic solvent for CSPE, toluene, xylene or solvent is used. The ratio of ethyl alcohol and aromatic solvent in the composition should be at least 1: 5. Additionally, the finished composition may contain an inorganic pigment (zinc oxide, chromium oxide, titanium dioxide, red iron oxide) in an amount of 2-6% (calculated on the finished composition).

An increase in the concentration of polymers in the solution, the proportion of ethyl alcohol in the composition of the mixed solvent, and the concentration of pigment in excess of these limits leads to a loss of stability of the composition (polymers precipitate in the idea of a swollen gel).

After the composition is cured, the interpolymer coating contains 7.5-20.0 parts by weight. the basis of PHMG and 92.5-80.0 parts by weight HSPE.

Composition JV ° 2. Composition based on HSPE and organically soluble salts of PHMG.

The purpose of composition N ° 2 is the same as composition Ks 1. The hydrophobic salts of PHMG and higher organic acids (oleate, pellargonate, undecylate) are dissolved in aromatic solvents; therefore, the composition is prepared in general for two solvent polymers.

The composition contains 0.7-l, 2m.h. hydrophobic salt of PHMG (oleate, pellargonate or undecylate) in the form of a 3.6-4.4% solution in an aromatic solvent (toluene, xylene, solvent) and 2.9-3, 2 wt.h. ChSPE in the form of a 3.6-4.4% solution in the same solvent. An increase in the concentration of polymers in the solution in excess of these limits leads to a rapid loss of viability of the composition (gelling).

After curing the composition, the interpolymer coating contains 18-28 parts by weight. salts of PHMG and 92.5-80 parts by weight HSPE. Composition JNsЗ. Composition based on isomers of polytrichlorobutadiene (PTCB) and PHMG base.

The composition is intended to protect equipment and communications of technical water supply, as well as surfaces operating in aggressive environments. The reacting polymers do not have a common solvent, therefore, the composition is prepared at the water-organic solvent interface.

The composition contains 2.8-2.9 wt.h. PGMG base in the form of a 4-5% solution in water and 2.3-2.4 wt.h. one of the isomers of PTCB in the form of a 4-5% solution in xylene. Hydrophobic film-forming polymers - PTCB isomers have MM - 50000-300000 conv.ed. and the structure of the repeating link:

[-CH ₂ -CH = CCl-CCl ₂ -] or [~ CH ₂ -CC1 = CC1-CHC1 ~]

1,1,2-PTXB 1,2,3-PTXB

An increase in the concentration of polymers in a solution in excess of these limits leads to irreversible crosslinking of the polymers and precipitation of the interpolymer.

After curing the composition, the interpolymer coating contains 43-45 parts by weight. base PGMG and 55-57 wt.h. PTCB.

Composition 4. Composition based on epoxy Dianova resin (ES) and the base PGMG.

The composition is intended for use as a biocidal sealing composition for protecting connecting nodes, seams, joints, etc. equipment and communications of technical water supply. Reactive polymers do not have a common solvent; the composition is prepared in small portions by mixing the components in bulk (without solvent) immediately before application to the prepared surface. The composition and the cured coating contain 30-35 parts by weight the base of the PHMG and 65-70mac.h. Diane ES with MM - 400-600. Composition JVs 5. Composition based on water-dispersive ES of POLYPOX E 260 W or POLYPOX E 2500/60 W brand and PHMG base.

The composition is intended to protect equipment and communications of technical water supply. Interacting polymers dissolve or disperse in water.

The composition contains 10-15 parts by weight the basis of PHMG in the form of a 15-23% aqueous solution, 20-26 wt.h. water-dispersive ES in the form of a 60% aqueous dispersion and 1.8-2.2 wt.h. 2,4,6-tris- (dimethylaminomethyl) phenol or salicylic acid.

To obtain the composition, water-dispersed dianic resins based on diphenylolpropane and epichlorohydrin with MM ~ 350-400 and an epoxy number of 22-25% (POLYPOX E 260 W) or with MM ~ 650-750 and an epoxy number of 10-12% (POLYPOX E 2500/60 W).

After curing the composition, the interpolymer coating contains 33-35 parts by weight. base PGMG and 67-65 parts by weight ES. Additionally, the finished composition may contain an inorganic pigment (zinc oxide, chromium oxide, titanium dioxide, red iron oxide) in an amount of 20-70% (calculated on the finished composition). An increase in the concentration of pigment in excess of these limits leads to a loss of stability of the composition.

Surface preparation, application methods and conditions for curing the compositions.

The necessary conditions for the prolonged disinfecting effect of interpolymer compositions 1-5 are the preparation of surfaces described below, the application and curing of the compositions described below. For room disinfection, the compositions according to examples 1.2 or 2.2 (biocide varnish) are applied to the surface of walls painted during the repair or construction of premises with oil or alkyd paint, but not earlier than 18-20 days after painting. In rooms already in use, the walls are thoroughly washed with warm soapy water and dried. Alkyd paints of the PF-115 type or alkyd varnish of the PF-283 type can be used as a primer on the surface of walls made of other materials.

Before use, the biocidal varnish is thoroughly mixed in the container of the manufacturer and applied to the walls in the premises with a brush, roller or pneumatic spray gun. On smooth surfaces (tile, surfaces painted with oil paint or primed), the composition is applied in one layer, and on rough (plastered, hardboard, etc.) - in two or three layers. The second and third layer is applied after drying the first layer at ambient temperature.

The varnish consumption rate: when applied by brush in one layer, 100-120 g / m ² , in three layers - 250-270 g / m ² ; when applied by pneumatic spraying, the varnish consumption in one layer is 120-130 g / m ² , in three layers ~ 350 g / m ² . The coating thickness in 1 layer is 5 microns, in 3 layers - 15 microns.

The coating is dried for at least 48 hours at a temperature of 20-30 ⁰ C, ventilating the room and observing fire safety rules. The control is the complete disappearance of the smell of the solvent.

To paint wooden structures and structures, the surface of the wood must be cleaned of bark, bast, various kinds of pollution. The machining of structures to be protected must be carried out before treatment with the biocidal composition.

Composition 1.2 before use is thoroughly mixed and applied in 2-3 layers on the prepared surface with a brush, roller, pneumatic spray; for small wooden parts - in bulk or by dipping. The second and third layers of the composition are applied after drying. previous layer at ambient temperature. The consumption rate of the composition for a single application: for a planed wooden surface of at least 150 g / m ² , for a non-planed wooden surface - at least 350-400 g / m ² .

To paint equipment operating in the aquatic environment (tanks, tanks, water conduits, etc.), the metal surface is cleaned with an emery cloth or sandblasting machine, degreased, applied and cured with an anti-corrosion primer. EP-0010 putty primer in 3 layers is applied as a primer for stainless steel equipment. For priming equipment made of steel 3, one of the systems is used: EP-0010 primer-putty (3 layers); enamel EP-0010 (1 layer) + enamel EP-773 (3 layers); VL-02 soil (2 layers) + XC-436 enamel (3 layers). For priming a concrete surface, EP-773 enamel (2 layers) or EP-0010 putty primer (2 layers) are used.

These primers for various surfaces are optimal: they protect the substrate from chemical corrosion, and also improve the compatibility of the biocidal composition with the surface to be protected. Biocidal compositions applied to an unprepared surface have low adhesion to certain surfaces; in the aquatic environment they do not completely protect the equipment from chemical and biological corrosion.

Biocidal compositions are applied to a fully cured epoxy coating no earlier than 7 days after epoxy coating. Reducing the exposure time may lead to swelling of the primer layer and peeling of the coating; longer aging is favorable.

Biocidal compositions are applied to the prepared surface with a brush, roller or pneumatic spray. When applied by pneumatic spraying, compositions 1, 2 and 3 can be diluted with an aromatic solvent, composition 5 with water. When using compositions 1, 2, 3, and 5 to protect equipment in an aqueous medium, the required efficiency and mechanical strength of the coatings is achieved by applying three to four layers of the composition, which provides an unpigmented coating with a thickness of 15-20 μm. Pigment can be added to compositions 1 and 5, then the coating strength increases, and its thickness is 80-120 microns.

When curing compositions 1, 2 and 3, each layer is incubated for 30-60 minutes at a temperature of 20-30 ⁰ C (ambient temperature), and then cured for 30-60 min at 50-80 ⁰ C; the final layer of the composition is cured for 2 hours at 80 ⁰ C.

Composition 4 (biocidal sealant) is applied to a metal, cement or concrete surface with a spatula in one layer with a thickness of 80-120 microns and cured at a temperature of 130-150 ⁰ C for 18-20 hours. Composition 5 is cured at a temperature of 130-150 ⁰ C for 1-3 hours. When curing bactericidal compositions under milder conditions, free PHMG is present in the water above the coating in excess of the maximum permissible concentration for drinking water.

For curing of small surfaces using a temperature-controlled oven; with large dimensions, the surface is heated by a heater of any type with a closed spiral, a technical hairdryer of the type Ferm HG-1500 (23Ov, 1500wt, 300-500 ⁰ C) or in special drying chambers.

The composition and deformation-strength characteristics of cured coatings are presented in table. 1. In contrast to coatings based on PGMG chloride, interpolymer coatings are non-sticky, have increased strength characteristics, are not soluble in water (varnished surfaces can be washed with water). The most durable and waterproof are coatings 4 and 5 (based on epoxy resins).

The following specific examples only illustrate the invention, but do not limit it. Also presented are data showing the prolonged disinfecting effect of coatings in air and water.

Industrial applicability

Example 1.1. A composition based on KhSPE and the foundation of PHMG for the protection of equipment in the aquatic environment and the protection of wood.

The composition contains 0.80 parts by weight. the basis of PHMG, 3.20 parts by weight of HSPE, 8.80 parts by weight of ethyl alcohol, 87.20 parts by weight toluene.

To prepare the composition, 8.9 g of PHMG chloride is dissolved in 10.9 g of hot water; the solution is cooled to room temperature and mixed with a solution containing 2.0 g of sodium hydroxide and 2.8 g of water. The reaction mass is stirred for 1 hour at room temperature. In the process of mixing the solutions, a white pasty substance is formed, which floats to the surface (PHMG base); it is separated from the mother liquor and washed with cold water. Get the base PHMG (8 g in terms of dry substance), which is dissolved in 88.0 g of ethyl alcohol.

32 g of ChSPE are dissolved in 872 g of toluene. The resulting solution was mixed at room temperature with a prepared solution of PHMG base in ethanol (ratio alcohol: total ~ 1: 10). The resulting solution was stirred for 1 hour. A homogeneous, slightly opalescent varnish with a nominal viscosity of 10-20 s (according to BZ-246-4, GOST 8420) is obtained, a dry residue of 4.0%, a pot life of ~ 3 months.

The varnish is applied on a metal surface primed with enamel EP-773 with a brush in 3-4 layers or pneumatic spray in three layers with a total coating thickness of 15 μm. Each layer is dried for 30-60 minutes at a temperature of 20-30 ⁰ C (ambient temperature), and then cured for 30-60 minutes at 50-80 C; the final layer of the composition is cured for 2 hours at 80 ⁰ C.

Get a colorless, uniform, transparent coating containing 20 wt.h. base PGMG and 80 wt.h. HSPE. Songs and coatings containing pigment have a color determined by the color of the pigment, a thickness of 50-70 μm and a spreading rate of 25-80 g / m ² in terms of dry film (according to GOST 8784). In the case of the expected contact of the coating with drinking water, the cured coating can withstand 3-5 days in tap water, which is changed every 24 hours.

The service life of the coating for water conservation and protection of equipment operated in long-term contact with water is at least 260 days (observation period) (Table 4). The content of free PHMG to the water above the coating does not exceed the maximum permissible concentration for drinking water (1 mg / l). Coating 1.1 also serves to disinfect water (Table 8) and protect wood (Table 3).

Example 1.2 Composition based on HSPE and PHMG base for prolonged disinfection of premises.

The composition contains 0.3 wt.h. base PGMG, 3.7 wt.h. KhSPE, 3.3 parts by weight ethyl alcohol, 92.7 parts by weight solvent.

The composition is prepared in the same way as in example 1.1. To obtain the basis of PHMG, a solution of 3.4 g of PHMG chloride in 4.1 g of water and 0.75 g of NaOH in 1.05 g of water are taken. Obtain 3.0 g of the base PHMG (calculated on dry matter). The polymer is dissolved in 33 g of ethyl alcohol and mixed with a solution of 37.0 g of ChSPE in 927 g of nefras (alcohol: nefras ratio = 1: 28). Get a colorless, uniform, slightly opalescent varnish with a dry residue of 4%, a conditional viscosity of 10-20 s (according to BZ-246-4, GOST 8420) and a viability of 12 months.

The composition for disinfection of rooms is applied to the prepared surface and cured in the same way as described in the section “Surface preparation, application methods and conditions for curing”

COMPOSITION). The coating is colorless, uniform, transparent, contains 7.5 parts by weight. base PGMG and 92.5 wt.h. HSPE. The service life of the coating is at least 21 months (observation period) (table. 2).

Example 2.1 Composition based on HSPE and PGMG oleate for the protection of equipment in the aquatic environment.

The composition contains 0.76 wt.h. oleate PGMG, 3.24 parts by weight KhSPE, 96 parts by weight xylene.

To prepare the composition, 3.2 g of PHMG chloride is treated with alkali in the same manner as described in Example 1. To the obtained PHMG base (2.88 g, calculated on dry matter), 5.04 g of oleic acid is added with stirring. The temperature of the reaction mixture rises to 40 ⁰ C, the reaction mixture acquires a yellowish color and a pasty consistency. To the obtained PHMG oleate (7.6 g, calculated on the dry matter), 30.4 g of xylene (solution concentration 20%) was added and stirred for 0.5 h.

32.4 g of ChSPE are dissolved in 929.6 g of xylene (solution concentration 3.4%) and the prepared solution of PHMG oleate in xylene is slowly added with stirring, stirred for 1 hour at a temperature of (25 ± 5) ⁰ C.

A homogeneous, slightly opalescent varnish is obtained with a dry residue of 4.0%, a nominal viscosity of ~ 100 s (according to BZ-246-4, GOST 8420) and a pot life of 6 months.

The composition is applied to the prepared surface and cured in the same way as in example 1.1. The polymer coating is colorless, uniform, contains 18 parts by weight. oleate PGMG and 82 wt.h. HSPE. For contact with drinking water, the cured coating can withstand 1 day in tap water. The service life of the coating during the preservation of drinking water and the protection of equipment is at least 13 months (observation period) (Table 5). In the water above the coating, pgmg oleate is absent. Example 2.2 Composition based on HSPE and pellargonate PGMG for prolonged disinfection of premises.

The composition contains 1.12 parts by weight pellargonate PGMG, 2.88 parts by weight KhSPE, 96 parts by weight nefras.

The composition is obtained in the same manner as in example 2.1. To obtain a base of PHMG, a solution of 4.7 g of PHMG chloride in 5.7 g of water and a solution of 1.1 g of NaOH in 2.6 g of water are mixed. The resulting PHMG base (4.2 g, calculated on the dry matter) was dissolved in 7.4 g of pellargonic acid. The obtained PHMG pellargonate (11.2 g calculated on the dry matter) is dissolved in 44.8 g of solvent and slowly added with stirring to a solution of 28.8 g of ChSPE in 915 g of solvent, stirred for 1 hour at a temperature of (25 ± 5) ⁰ C. A homogeneous, slightly opalescent varnish is obtained with a dry residue of 4.0%, a nominal viscosity of ~ 150 s (according to BZ-246-4, GOST 8420), and a viability of 6 months. The composition is applied to the prepared surface and cured as described in example 1.2.

The polymer coating is colorless, uniform, contains 28 parts by weight. PGMG pellargonate and 72 parts by weight HSPE. The service life of the coating during the disinfection of the premises is at least 21 months from the day of application (observation period) (Table 2).

Example 3. Composition based on PTCB isomers and PHMG base.

12.2 g of PHMG chloride are treated with alkali in the same manner as in Example 1, and 10.2 g of PHMG base are obtained (calculated on dry matter). The base is dissolved in 276 ml of water, mixed with a solution of 9 g of 1,1,2-PTXB or 1,2,3-PTCB in 180 g of xylene, add 0.1 N NaOH to pH = 10 and mix vigorously for 60 minutes. The resulting two-phase system is defended in a separatory funnel until complete separation. The lower layer is separated, washed with water until neutral, dried over calcium chloride and filtered. Get a black solution with a nominal viscosity of 40-50 s (according to BZ-246-4, GOST 8420); viability of 12 months.

The composition is applied to the prepared surface in three layers; each layer is dried for 30-60 minutes at a temperature of 20-30 ⁰ C (ambient temperature), and then cured for 30-60 minutes at 50-80 ⁰ C; the final layer of the composition is cured for 2 hours at 80 ⁰ C.

Get a smooth, uniform coating of black color, a thickness of 15-20 microns. The coating retains water resistance and biocidal action for at least 6 months (observation period).

Example 4. Biocidal sealing composition based on the ED-20 brand and the base of the PGMG.

To prepare the composition, 36.8 g of PHMG chloride is treated with alkali as described in Example 1. The base of PHMG obtained in the form of a paste-like mass (33 g, calculated on the dry matter) is mixed with 67 g of ED grade ED-20. The pot life of the composition is 0.5 hours.

The composition is applied to a surface of metal, cement or concrete with a spatula in one layer with a thickness of 80-120 microns and cured at a temperature of 130-150 ⁰ C for 18-20 hours. A white coating with an uneven surface is obtained. The coating retains biocidal action in the aquatic environment for at least 1 year (observation period).

Example 5.1. Composition based on water-dispersive ES of POLYPOX E 260 W brand and PHMG base.

36.8 g of PHMG chloride is treated with alkali as described in Example 1. The obtained PHMG base is dissolved in 39.6 g of water and 5.2 g of 2,4,6-tris (dimethylaminomethyl) phenol and 166.7 are slowly added with stirring. g water-dispersive ES brand POLYPOX E 260 W. The composition is colorless, conditional viscosity (according to BZ-246-4, GOST 8420) 50-60 s, viability 18-24 hours. The composition is applied with a brush on a metal surface primed with 3 layers of EP-0010 putty, in 2-3 layers with a thickness of 50 μm and cured at a temperature of 130-150 ⁰ C for 1-3 hours. A uniform, colorless coating with a thickness of 15-20 μm is obtained, which retains biocidal properties in the aquatic environment for at least 8 months (observation period) (Table 6). Example 5.2. Pigmented composition based on water-dispersive ES of the POLYPOX E 260 W brand, PHMG base and titanium dioxide.

In 100 g of the composition obtained in Example 5.1, 35 g of titanium dioxide are dispersed in a bead mill for 1 hour to a milling degree of 30 μm using a wedge device. Get a white biocidal paint with a conditional viscosity (according to BZ-246-4, GOST 8420) 70-100 s; hiding power of the pigmented composition in terms of dry film (according to GOST 8784) 40-70 g / m ² . The paint is applied to the prepared surface and cured in the same way as in example 5.1. The coating thickness is 80-120 microns, biocidal action is similar to example 5.1.

Changing the composition beyond the stated limits.

A decrease in the content of the PGMG derivative in the compositions below the amount indicated in the examples leads to a decrease in the effectiveness of the action of the biocide coating; increase - to the deterioration of the water resistance of the coating in compositions for the aquatic environment; in compositions for disinfection of premises, this is impractical for economic reasons. An increase in the concentration of reactive polymers in solutions in excess of these limits leads to a loss of stability of the composition; a decrease in the concentration of polymers is impractical for economic reasons. Table 1

The composition and deformation-strength characteristics of interpolymer coatings according to examples 1-5.

* _ coatings additionally contain pigment table 2

The prolonged disinfecting effect of the compositions according to examples 1.2 and 2.2 when processing surfaces in rooms *

* Tests were carried out in accordance with ((Regulatory indicators of the safety and effectiveness of disinfectants to be monitored during mandatory certification) N ° 01-12 / 75 of 1997; “Test methods for disinfectants to assess their safety and effectiveness)), Moscow, MH RF 1998, parts I and II ”/.

Table 3

The effectiveness of the protection of wet and dry wood with a disinfectant according to example 1.1 *

" ^• Tests were carried out according to GOST 30028.4-93

Note 1: 1 group: Repository-shhlopop, Aspergillis faris, Fisarit topilit, Repillitus-sarcot, Fitarit pheerispositoliteli,

Group 2: Fisariit javapisit, Fisariit teristoides, Roesulotuses variotti, Sroridestiit sladosrorioides, Trishosroriit sheterotorrhit, Asrergillis heppebergil, Dissila ripisola, Sladosroriit herbarit, Vertisilliit tarqiapdi;

Group 3: Aspergillis atheidapit, Repilitus susloriit, Alteparia tepis, Relilaparilliaps, Fisarit syrtit, Repillitrit, Irrigation, Note 2: 1 point - visually clean samples; when examined under a microscope, small foci are visible in the form of spots of one type of wood-staining or mold fungi; sporulation stage is absent; 2 points - superficial development of mycelium of certain types of wood-staining and mold fungi in the form of spots; sporulation stage is absent; 3 points - abundant development of mycelium of certain types of wood-staining or mold fungi; the beginning of the sporulation stage of one of the species of fungi; 4 points - the growth of mushrooms is clearly visible during visual inspection, various stages of maturation of most species of wood-staining and mold fungi; 5 points - a deep lesion with wood-coloring and mold fungi of the entire area of the sample, intensive sporulation. Table 4

The prolonged disinfecting effect of the composition according to example 1.1 when preserving water and disinfecting the surface of the equipment *

* Tests were carried out according to: GOST 18963-73 “Drinking water. Methods of sanitary and bacteriological analysis "; MUK 4.2.671-97 "Methods of sanitary-microbiological analysis of drinking water";"The method of measuring the mass concentration of PHMG chloride in water by the photometric method" MVI JNg 242 / 07-2005 of 28.03. 2005 Table 5

The prolonged disinfecting effect of the composition according to example 2.1 when preserving water and disinfecting the surface of the equipment

Table 6

The prolonged disinfecting effect of the composition according to example 5.2 when preserving water and disinfecting the surface of the equipment.

Table 7

The increase in the total microbial number during storage of control tap water and water containing added PHMG chloride

Table 8

The effectiveness of the disinfection of tap water contaminated with test microorganisms, the coating according to example 1.1 *

* The initial concentration of test microorganisms in 0.9-l, 2xl0 ⁵ cfu / 100 ml.

Claims

CLAIM

1. A method for prolonged disinfection of premises, equipment, preservation and disinfection of water, including: a) obtaining a derivative of polyhexamethylene guanidine in the form of a base or an organic salt in the form of oleate, pellargonate, undecylate from polyhexamethylene guanidine chloride; b) preparing a solution of the polyhexamethylene guanidine derivative indicated in (a) in water or an organic solvent; c) preparing a solution of a hydrophobic film-forming polymer selected from the group consisting of chlorosulfonated polyethylene, polytrichlorobutadiene in an organic solvent; g) the formation of an interpolymer disinfectant composition, combined under stirring conditions, 0.3-3.9 wt.h. 3.6-9.0% solution of the specified hydrophobic polymer; d) applying to the previously prepared coating surface of an interpolymer disinfectant composition from step g), if necessary, in the form of a composition containing target additives; 5–20 µm thick non-pigmented coating, possibly in several layers; f) drying of each coating layer first at ambient temperature and its subsequent final curing is possible at a temperature of 50-80 ⁰ C, and the ratio between the derivatives of polyhexamethylene guanidine and the hydrophobic polymer in the cured interpolymer (coating) is 7.5-45.0, respectively parts by weight and 92.5-55.0 parts by weight

2. A method for prolonged disinfection of premises, equipment, preservation and disinfection of water, including: a) obtaining a base of polyhexamethylene guanidine from polyhexamethylene guanidine chloride; b) the formation of an interpolymer disinfectant composition when combined under conditions of mixing 10-35 wt.h. the base of polyhexamethylene guanidine from stage a) in the form of a 15-23% solution in water or without solvent, with 20-65 wt.h. epoxy resin in the form of a 60% solution in water or without solvent, if necessary in combination with a hardener for it; c) applying to a previously prepared surface an interpolymer disinfectant composition, possibly in the form of a composition containing target additives, with a thickness of 15-120 microns; g) subsequent curing of the coating at 130-150 ⁰ C and the ratio between the derivatives of polyhexamethylene guanidine and epoxy resin is in the range of 32-34 and 66-68 wt.h.

3. The method of prolonged disinfection according to claim 1, characterized in that in the case of contact of the coating with drinking water, a chemically unbound derivative of polyhexamethylene guanidine is extracted with water from the cured coating.