PL210155B1 - New quaternary gemini-type compound and application of the new quaternary gemini-type compound in concentrate of an agent for maintenance of wood - Google Patents

Description

Description of the invention

The subject of the invention is a new quaternary hydroxyammonium glycol ester compound of the gemini type and its use in a water-dilutable wood preservative concentrate with highly biocidal properties and deep penetration into the depths.

Gemini type compounds are already known from the patent literature. They are also called dimeric or twin compounds because they contain two identical hydrophobic chains, two identical polar groups and a linker also called a bridge.

Gemini most often act as emulsifiers and surfactants. The patent literature, own tests and experiments show that compared to classic surfactants with one hydrophobic group and one hydrophilic group, gemini surfactants with at least two hydrophobic groups and at least two hydrophilic groups are several times more effective in reducing surface tension and surface activity at interfaces. Additionally, in combination with classic surfactants, gemini surfactants show synergistic properties in lowering surface tension, foaming ability, solubilizing, emulsifying, and especially penetrating into various porous materials.

In US Patent Nos. 6,666,217, 6,777,384, 6,797,687, 6,805,141, 6,919,305, gemini surfactants have been described, where the bridge is polyethylene glycol and the alkyl is of petrochemical origin.

JP 2006 315 987 discloses a hair washing composition where a cationic gemini compound exhibits hair protective properties.

WO 0 123 515 and US 6 358 914 describe washing compositions containing cationic gemini compounds.

The authors of the patent EP 1 689 444 describe a biologically active preparation containing the cationic compound gemini, used in skin diseases and metabolic diseases.

On the other hand, in the patent description No. WO 9 731 890 the cationic compound gemini was used as an emulsifier in cleaning agents and cosmetic preparations.

Quaternary ammonium compounds, mainly as washing and biocidal compounds, have also been known on the market for a long time.

The authors of the patent No. EP 1 796 739 describe a disinfecting composition based on a quaternary ammonium compound.

US Patent No. 6,462,014 describes a low-foaming cleaning composition comprising at least one alkoxylated quaternary ammonium compound and at least one non-ionic surfactant based on branched, 3-12 mole ethylene oxide ethylene oxide based alcohols.

In contrast, in WO 00/62 937 a quaternary ammonium compound was used as a flocculant in the separation of silicates from iron ores.

In turn, patent no. WO 2006/097 672 teaches the composition of a disinfectant composition containing at least one ammonium quaternary compound, the action of which is supported by one or more nonionic surfactants and, optionally, very little organic solvents. This composition is very effective against Staphylococcus aureus, Salmonella choleraesuis and Escherichia coli.

In WO 0 154 502, a quaternary ammonium compound in a concentration greater than 10% by weight was dissolved in alcohol or other non-toxic solvent, and thus a preparation against microbial growth on food was obtained, mainly applied by spraying in the form of steam for 0.1 a second.

The biocidal properties of quaternary ammonium compounds were also used in the formulation of wood impregnations.

US Patent No. 6,262,097 describes a wood preservative composition containing quaternary ammonium salts aided by isothiazolone derivatives.

WO 2007/005 195 describes a wood preservative composition consisting of at least one metal corrosion inhibitor, a quaternary ammonium compound, at least two amines, a pH stabilizing agent between 7.1 - 8.5 and water.

The authors of US patent 5,730,907 tested a wood impregnation containing a biocide in the form of a quaternary ammonium salt (e.g., didecyldimethylammonium chloride) supplemented with isothiazolone or isophthalonitrile and enriched with antioxidants.

PL 210 155 B1

US 2006/0 251 915 discloses a tree protective composition comprising a long chain alkyl quaternary ammonium compound containing 16 to 50 carbon atoms, additionally containing at least one nitrogen, oxygen, sulfur or any halogen atom.

In the next patent application No. US 2005/0 124 723 the authors checked the biocidal effectiveness of a non-aqueous wood impregnation containing from 0.5 to 50 parts of a biocidal quaternary ammonium compound, from 0.5 to 50 parts of an aliphatic or cycloaliphatic carboxylic acid containing from 6 to 30 atoms. carbon, 0 to 5 parts additional biocides, 0 to 20 parts pigments and stability enhancers, 40 to 99 parts non-polar organic solvent. The ratio of ammonium compounds to carboxylic acids is between 1: 3 to 3: 1.

The authors of the patent application US 2005/0 000 387 describe an aqueous wood impregnation based on quaternary ammonium salts supplemented with basic copper compounds, a soluble nitrite salt and a dicarboxylic acid.

U.S. Patent Application No. , copper sulfate pentahydrate and others.

Wood impregnations can also be based on other compounds known for their biocidal properties.

In the patent application No. US 2006/0 257 578 a microemulsion formed on the basis of zinc borate is presented, the average particle size of which is 0.21 µm. Boron compounds are known for their biocidal properties, additionally, boron in inorganic compounds has a fire-retardant effect.

U.S. Patent No. 7,128,778 describes a wood preservative composition containing boron compounds and silicone compounds. Optionally, it may contain at least one solvent such as, for example, tetrahydrofuran, pentane, water, and the like.

US Patent No. 6,896,908 discloses a boron-based wood impregnation concentrate additionally containing biocidal metal compounds, such as, for example, copper or zinc. The preparation additionally contains organic acids, free ammonia or its derivatives.

WO 2005/007 368 describes an aqueous wood protection composition based on incompletely soluble copper compounds. Examples are copper hydroxide, basic copper carbonate, copper carbonate, basic copper sulfate, basic copper nitrate, copper oxychloride, copper borate, basic copper borate, or mixtures thereof.

Copper compounds have also been used in the impregnation described in US Patent Application No. 2006/0 162 611. The formulation is mainly based on copper carbonate and alkanolamines, such as monoethanolamine, and supplemented with phosphonates and ethylenediamine derivatives.

US Patent No. 7,198,663 describes a tree protective composition consisting of inorganic polymers, additionally containing Al2O3 in an amount of 3.8 - 7.0%, ZrO2 in an amount of 5.25 - 9.1%, CuO in an amount of 0.7 - 8.8% and a buffering agent, e.g. acetic acid or sodium acetate. The pH of the composition was maintained between 2 and 4.

The authors of WO 2004/011 215 disclose a polymeric wood preservative composition containing metal ions complexed in ethanolamines, polyethyleneimines, ammonia or mixtures thereof, and / or in polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidine and / or polyisopropylacrylamide.

U.S. Patent No. 6,319,431 discloses a fire-retardant and biocidal wood preservative containing a urea solution and sources of inorganic acid groups such as phosphoric acid, mono- or diamine phosphate, a water-miscible alcohol, e.g. methanol or ethanol, and inorganic borates, such as e.g. acid. boric or borax.

WO 2007/064 236 describes a wood impregnation containing new boron compounds called boratrons, which are obtained from epoxidized vegetable oils, boric acid and diisopropanolamine. Boron in this compound, additionally supported by quaternary ammonium compounds, shows high resistance to leaching.

PL 210 155 B1

In turn, in the Polish patent description No. PL 185 079, the American equivalents of which are US patents 6 180 672 and US 6 362 370, a biocidal wood preservative is presented, containing at least one quaternary ammonium compound, one or more other biocides, which at least one copper and / or zinc compound and excipients including antifoams, antioxidants, dyes or fragrances.

Wood impregnations are chemical preparations that bind to the surface of the wood by ion exchange and penetrate into its structure. A good biocidal and fire-retardant impregnation should be characterized by:

- High toxicity to tree-destroying organisms

- The harmlessness of action on the tree itself and on other materials (screws, nails, etc.)

- No deterioration of the mechanical properties of the tree

- Harmless to humans, animals and the environment

- Durability of staying in wood

- Deep penetration into the wood

- Delaying the ignition of the material

- Reduction of the speed of flame spread and the combustion process itself

- No emission of toxic substances and unpleasant smell

The standard PN-EN 335-1 provides a general classification of the degradation risk, which includes 5 classes. For each class, the hazards of the basic wood-destroying factors were determined.

Polish requirements for the chemical protection of construction timber are included in the instruction of the Building Research Institute No. 355/98. The instruction introduces differentiation of the number of degrees of wood hazard caused by domestic fungi, mold fungi and wood-destroying insects. It also specifies the parameters of wood saturation with the preservative.

The PN-EN 350-02 standard provides a classification of wood's susceptibility to saturation.

Several methods can be used to impregnate wood with impregnating agents:

- pressureless impregnation - at atmospheric pressure;

- pressure impregnation - at which the maximum pressure value reaches 200 kPa;

- surface impregnation, where the preparation applied to the wood surface penetrates to a depth of 2-4 mm;

- deep impregnation, which includes methods in which the wood becomes saturated above 8 mm.

The commonly used methods of wood impregnation include non-pressure methods:

- saturation with the lubrication method, where the wood is lubricated with brushes, brushes or rollers;

- impregnation by spraying, where the wood is sprayed 2-3 times with a spray device;

- saturation with the pouring method, where the wood is poured in special tunnels and the wood is moved on rollers;

- impregnation by the baking method, where the wood is immersed in an impregnating agent.

Depending on the type of bath, method and applied parameters of the bath, different saturation effects can be achieved, e.g. surface or deep.

The aim of the invention is to provide a water-borne wood preservative concentrate with highly biocidal properties and deep penetration into the wood. This feature is important because the lack of even and deep saturation of the wood with the impregnating agent may cause rotting of some parts of the wood, while the remaining ones will be well preserved.

It has surprisingly been found that the new quaternary gemini compounds which contain a hydroxyl group on the second carbon atom from the quaternary nitrogen enable very deep saturation of the wood. Additionally, it has been found that these hydroxyl quaternary gemini compounds are capable of transporting other biocidal compounds deep into the tree, in particular boron compounds and non-ferrous metals.

PL 210 155 B1

The novel gemini quaternary hydroxyammonium glycol ester of the invention contains at least two hydroxyl groups and is represented by the general formula:

where R and R4 is an alkyl group of more than 2 carbon atoms, R1 and R3 is an alkylene or hydroxyalkylene group of more than 5 carbon atoms, R2 is hydrogen or a methyl group, R5, R6, R8 and R9 are the same or different and represent a substituted alkyl group , hydroxyalkyl, cycloalkyl or alkenyl of up to 12 carbon atoms, aryl or alkylaryl or together with the nitrogen may form 5 or 6 membered rings, optionally containing oxygen and / or sulfur and / or nitrogen heteroatoms, R7 and R10 may be the same or different and are hydrogen, a substituted alkyl, hydroxyalkyl, cycloalkyl or alkenyl group of up to 12 carbon atoms, an aryl or alkylaryl group, R11 is an alkyl group with a carbon atom content of 1 to 12, or a hydroxyalkyl group with a carbon content of 2 to 12 , m and p are independently from 1 to 3, and n is an integer greater than 1.

The wood preservative concentrate according to the invention is characterized in that it comprises a novel gemini quaternary hydroxyammonium glycol ester containing at least two hydroxyl groups and is represented by the general formula:

(1Π4 ρ) ⁺ (ιη ι ρ) Η | | Ct X 5 - where R and R4 is an alkyl group of more than 2 carbon atoms, R1 and R3 is an alkylene or hydroxyalkylene group of more than 5 carbon atoms, R2 is hydrogen or a methyl group, R5, R6, R8 and R9 are the same or different, and represent a substituted alkyl, hydroxyalkyl, cycloalkyl or alkenyl group of up to 12 carbon atoms, an aryl or an alkylaryl group, or can form together with the nitrogen atom 5 or 6 membered rings, optionally containing oxygen and / or sulfur and / or nitrogen heteroatoms, R7 and R10 may be the same or different and represent hydrogen, substituted alkyl, hydroxyalkyl, cycloalkyl or alkenyl group of up to 12 carbon atoms, aryl or alkylaryl group, R1 is an alkyl group with 1 to 12 carbon atoms or a hydroxyalkyl group containing carbon atoms from 2 to 12, m and p are each independently from 1 to 3, and n is an integer greater than 1.

It is preferred that the wood preservative concentrate according to the invention contains organic and inorganic boron compounds, preferably polyborates of alkanolamines and / or amines, in an amount of up to 10% by weight, based on boron.

It is preferred that the wood preservative concentrate according to the invention contains organic and / or inorganic copper compounds in an amount of up to 10% by weight, based on copper.

It is preferred that the wood preservative concentrate according to the invention contains organic and / or inorganic zinc compounds in an amount of up to 10% by weight, based on the zinc.

It is preferred that the wood preservative concentrate according to the invention contains other biocidal compounds in an amount up to 10% by weight, preferably benzimidazole derivatives, mercaptobenzothiazole derivatives, isothiazolones, sulfonamides, triazoles, thiophosphates, dithiocarbamates, haloacetic acids, their amides, phenols, chlorophenols and others.

PL 210 155 B1

It is preferred that the wood preservative concentrate according to the invention contains water-miscible organic solvents in an amount of up to 25% by weight, preferably lower alcohols and glycols, their esters and ethers.

It is preferred that the wood preservative concentrate according to the invention contains antifoams in an amount of up to 0.5% by weight.

It is preferred that the wood preservative concentrate according to the invention contains antioxidants in an amount up to 1% by weight.

It is preferred that the wood preservative concentrate according to the invention contains fragrances in an amount of up to 1% by weight.

It is preferred that the wood preservative concentrate according to the invention contains the control dye in an amount of up to 1% by weight.

It is important that the newly developed wood preservative concentrate meets all the technical requirements for such a preparation.

Initial tests showed that the known quaternary ammonium compounds of the gemini type bind to the wooden substrate in a permanent manner, which in this case turned out to be a disadvantage because it prevented deep penetration of the biocidal active substance into the substrate.

It was surprisingly found that the penetration depth increases dramatically when using a new quaternary hydroxyammonium glycol ester gemini containing at least two hydroxyl groups. In addition, the penetration depth increases when we use carboxylic acids with carbon atoms content from 2 to 12, aliphatic or aromatic, straight or branched, which may additionally contain amino, sulfonic and hydroxyl groups as an anion. The most preferred anions turned out to be: lactate, hydroxyacetic, hydroxybenzoic, 2-aminopropionate, 3-aminopropionate.

The subject matter of the invention will be explained in more detail in the following examples without limiting its scope.

The examples show aqueous concentrates according to the invention which, when diluted with water in a ratio of 1: 5 to 1:20, are used to preserve the tree.

P r z k ł a d 1.

parts by weight of 35% hydroxyammonium glycol ester gemini represented by formula 1, where R and R4 is C4 - C6 alkyl, R1 and R3 is C6 - C9 alkylene, R2 is hydrogen, R5, R6, R8 and R9 is hydroxyethyl, R7 and R10 is methyl, R11 is hydroxyethyl, m and p are from 1.3 to 1.6, and n is 3, mixed with 0.01 parts by weight of sunlight resistant green dye and made up to 100 parts by weight with water.

P r z k ł a d 2.

parts by weight of the quaternary gemini compound of Example 1 parts by weight of an alkanolamine polyborate with 10 parts by weight of boron parts by weight of water.

P r z k ł a d 3.

parts by weight of the quaternary gemini compound of Example 1 parts by weight of the reaction product of citric acid, alkanolamine and zinc oxide. The reaction product contained 10 parts by weight of zinc.

parts by weight of water.

P r z k ł a d 4.

parts by weight of the gemini quaternary compound of Example 1 parts by weight of the reaction product of fumaric acid, alkanolamine and copper hydroxide. The reaction product contained 7 parts by weight of copper and parts by weight of water.

P r z k ł a d 5.

parts by weight of the quaternary gemini compound of Example 1 parts by weight of alkanolamine polyborate and dimethylpropylamine. The reaction product contained 10 parts by weight of boron, parts by weight of the reaction product of maleic acid, alkanolamine and basic copper carbonate. The reaction product contained 6.5 parts by weight of copper parts by weight of the reaction product of fumaric acid, alkanolamine and zinc oxide. The reaction product contained 9 parts by weight of zinc and parts by weight of water.

PL 210 155 B1

P r z k ł a d 6.

parts by weight of the quaternary gemini compound of Example 1 parts by weight of an alkanolamine polyborate with 10 parts by weight of boron parts by weight of the reaction product of edetic acid, alkanolamine and basic copper carbonate. The reaction product contained 8 parts by weight of copper parts by weight of the reaction product of edetic acid, alkanolamine and zinc oxide. The reaction product contained 10 parts by weight of zinc, parts by weight of isothiazolone under the trade name Kathon, 930 parts by weight of water.

P r z k ł a d 7.

parts by weight of the quaternary gemini of Example 1 parts by weight of an alkanolamine polyborate with 10 parts by weight of boron parts by weight of the reaction product of tartaric acid, alkanolamine and copper hydroxide. The reaction product contained 8 parts by weight of copper parts by weight of the reaction product of tartaric acid, alkanolamine and zinc oxide. The reaction product contained 10 parts by weight of zinc, parts by weight of isothiazolone under the trade name Kathon WT, parts by weight of butylglycol, parts by weight of water.

The above concentrates were diluted with process water in the ratio 1: 9, as in the majority of wood preservatives available on the market.

Suitable woods were preserved by conventional methods such as painting, spraying, spraying, and impregnating by cold and hot and cold bath methods.

In all comparable cases, there was a 2-3 times greater increase in penetration into the tree and more than twice as much increase in the absorbed wood preservative according to the invention, which proves the high efficiency of the newly developed water-dilutable concentrate containing the newly discovered quaternary hydroxyammonium-glycol-ester gemini type compound .

Claims (11)

1. A new gemini type hydroxyammonium glycol ester quaternary containing at least two hydroxyl groups and is represented by the general formula: where R and R4 is an alkyl group of more than 2 carbon atoms, R1 and R3 is an alkylene or hydroxyalkylene group of more than 5 carbon atoms, R2 is hydrogen or a methyl group, R5, R6, R8 and R9 are the same or different and represent a substituted alkyl group , hydroxyalkyl, cycloalkyl or alkenyl of up to 12 carbon atoms, aryl or alkylaryl or together with the nitrogen may form 5 or 6 membered rings, optionally containing oxygen and / or sulfur and / or nitrogen heteroatoms, R7 and R10 may be the same or different and are hydrogen, a substituted alkyl, hydroxyalkyl, cycloalkyl or alkenyl group of up to 12 carbon atoms, an aryl or alkylaryl group, R11 is an alkyl group with a carbon atom content of 1 to 12, or a hydroxyalkyl group with a carbon atom content of 2 to 12 , m and p are independently from 1 to 3, and n is an integer greater than 1. PL 210 155 B1 2. Wood preservative concentrate, characterized in that it comprises a novel gemini-type hydroxyammonium glycol ester quaternary containing at least two hydroxyl groups and has the general formula: where R and R4 is an alkyl group of more than 2 carbon atoms, R1 and R3 is an alkylene or hydroxyalkylene group of more than 5 carbon atoms, R2 is hydrogen or a methyl group, R5, R6, R8 and R9 are the same or different and represent a substituted group alkyl, hydroxyalkyl, cycloalkyl or alkenyl of up to 12 carbon atoms, an aryl or alkylaryl group or together with the nitrogen may form 5 or 6 membered rings, optionally containing oxygen and / or sulfur and / or nitrogen heteroatoms, R7 and R10 may be alone or different and represent hydrogen, a substituted alkyl, hydroxyalkyl, cycloalkyl or alkenyl group of up to 12 carbon atoms, an aryl or alkylaryl group, R11 is an alkyl group with carbon atoms from 1 to 12, or a hydroxyalkyl group with carbon atoms from 2 to 12, m and p independently of each other take a value from 1 to 3 and n is an integer greater than 1. 3. A wood preservative concentrate according to claim 1; A process as claimed in claim 2, characterized in that it may contain as a supplement organic and inorganic boron compounds, preferably polyborates of alkanolamines and / or amines, in an amount of up to 10%, based on boron. 4. A wood preservative concentrate according to claim 1; A process as claimed in any of claims 2 to 3, characterized in that it may additionally contain copper compounds in an amount of up to 10% by weight, based on copper. 5. A wood preservative concentrate according to claim 1; A composition according to any of the claims 2 to 4, characterized in that it may contain as a supplement organic and inorganic zinc compounds in an amount of up to 10% by weight, based on zinc. 6. A wood preservative concentrate according to claim 1; A method according to claims 2 to 5, characterized in that it may contain as a supplement other biocidal compounds in an amount up to 10% by weight, preferably benzimidazole derivatives, mercaptobenzothiazole derivatives, sulfonamides, triazoles, thiophosphates, dithiocarbamates, haloacetic acids, their amides, phenols, chlorophenols and others. 7. A wood preservative concentrate according to claim 1, A process as claimed in any of claims 2 to 6, characterized in that it may additionally contain water-miscible organic solvents in an amount of up to 25% by weight, preferably lower alcohols and glycols, their esters and ethers. 8. A wood preservative concentrate according to claim 1, A process according to any of the claims 2 to 7, characterized in that it may contain antifoams in an amount up to 0.5% by weight as a supplement. 9. A wood preservative concentrate according to claim 1; A composition according to any of the claims 2 to 8, characterized in that it may contain antioxidants in an amount of up to 1% by weight as a supplement. 10. A wood preservative concentrate according to claim 1, A composition according to any of the claims 2 to 9, characterized in that it may contain fragrances in an amount of up to 1% by weight as a supplement. 11. A wood preservative concentrate according to claim 11, A method according to any of the claims 2 to 10, characterized in that it may contain as a supplement a control dye in an amount of up to 1% by weight.