NO843272L - AFFICIENT WOOD PROTECTION AGENT - Google Patents

Abstract

1. An aqueous wood preservative based on an aqueous solution of an amino-containing low molecular weight 1,3-butadiene polymer which dries oxidatively and has been randered soluble with an acid, and having a pH of from 2 to 6, characterized in that it contains 4-[3-(4-n-butyldimethylsilylphenyl)-2- methylpropyl]-cis-2,6-dimethylmorpholine, 4-[3-(4-t-butylphenyl)-2-methylpropyl]-cis-2,6 -dimethylmorpholine or 4-tridecyl-2,6-dimethylmorpholine in dissolved form.

Description

The present invention relates to an aqueous wood preservative containing an oxidatively drying,

with acids solubilized, low molecular weight 1,3-butadiene polymer containing amino groups, and which a pH value of 2-6 dissolves in water, and a water-insoluble active substance in aqueous solution.

It is known that water-soluble alkaline binders

can be dissolved in water together with water-insoluble active substances and used as a wood preservative (BRD official document 30 14 194). These aqueous solutions have the disadvantage that they cause the wood fibers to swell at a pH value of

8-12. With this swelling, the penetration of the aqueous solution and thus of the active substance into the wood is prevented.

Furthermore, it is known to produce aqueous wood preservatives from water-soluble active substances and oxidatively drying, acid-solubilized, low molecular weight 1,3-butadiene polymers which contain amino groups and which dissolve in water at a pH value of 2-6 (EP-B-9546 ).

It was now found that aqueous wood preservatives based on an aqueous solution of an oxidatively drying,

with acids solubilized, low molecular weight 1,3-butadiene polymer

which contains amino groups and which, at a pH value of 2-6, contains a water-insoluble active substance in dissolved form,

does not prevent the penetration of the active substance into the wood.

It is surprising that the compound 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine in the aqueous solution of the oxidatively drying acid-solubilized , low molecular weight 1,3-butadiene polymer which contains amino groups, and which dissolves in water at a pH value of 2-6, while it is not or only slightly soluble in the known aqueous solution of a neutralized alkyd resin.

In principle, all organic and inorganic acids will be suitable for reaction with the amino groups in the 1,3-butadiene polymer.

Preferably, acids are used which provide storage-stable formulations, for example phenyl-4-sulphonic acid, toluenesulphonic acid and other substituted mono- or polynuclear aromatic sulphonic or carboxylic acids, amidosulphonic acid, alkanoic acids such as formic acid, acetic acid, inorganic acids, for example hydrochloric acid, sulfuric acid, including carbonic acid.

With regard to the improvement of the impact can also

acidic compounds which in themselves provide a protective effect are used for reaction with the amino groups, for example fluoroboric acid, boric acid, hexafluorosilicic acid, hydrofluoric acid.

The water-insoluble active substances, especially water-insoluble organic active substances retain their known good effect in the aqueous solution. The new wood preservatives contain, for example, calculated on the finished mixture, in aqueous solution 0.5-5% by weight, especially 1-4% by weight, of a water-insoluble active substance and 3-50% by weight, especially 5-20% by weight, oxidative drying, acid-solubilized, amino group-containing, low molecular weight 1,3-butadiene polymer which dissolves in water at a pH value of 2-6.

Fungicidal active substances which are insoluble in water, especially water-insoluble organic active substances for the wood preservative according to the invention are, for example, 4-[3-(4-trimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine, b.p. 145-147°C/0.07 mbar.

4-[3-(4-(i)-propyldimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine.

4-[3-(4-(n)-butyldimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-23

dimethylmorpholine, nQ = 1.4950.

4-[3-(4-(i)-butyldimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine.

4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

(Fenpropimorph)

4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-piperidine 4-tridecyl-2,6-dimethylmorpholine (Tridemorph)

N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid amide

(Furmecyclox)

Metal salts (for example aluminum salt or stannous salt) of N-hydroxy-N-cyclohexyl diazenium oxide

Bis-(tributyl)tin oxide (TBTO)

2-(Methoxycarbonylamino)-benzimidazole (Carbendazim) 1-[2-(2,4-dichlorophenyl)-1,3-dioxolon-2-yl-methyl]-1H-1,2,4-triazole (Azaconazole)

1-[2-(2,4-Dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole.

1-[2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole.

Bis-phenyl-(3-trifluoromethyl-phenyl)-1-(1,2,4-triazolyl)-methane. 1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone. 3-(4-Chlorophenoxy)(1,1-dimethylethyl)-1H-1,2,4-triazolyl-1-ethanol.

1-(2,4-Dichlorophenoxy)-3,3-dimethyl-1(1H)-1,2,4-triazol-1-yl)-1-butene.

To improve the effect, the new wood preservatives can also contain insecticides, for example chlorinated hydrocarbons, carbamates or phosphoric acid esters.

Of these active substances, gamma-hexachlorocyclohexane is preferred. The new wood preservatives contain, for example, 0.2-2% by weight, especially 0.3-1% by weight, of insecticidal substances.

In order to improve the fungicidal effect, the new wood preservatives can also contain known water-soluble fungicides, for example alkali salts of N-hydroxy-N-cyclohexyldiazenium dioxide, for example in amounts of 0-2% by weight, especially 0.3-1% by weight. The new wood preservatives may also contain surfactants,

for example alkylene oxide addition products, for example ethylene oxide or propylene oxide addition products, especially to alkylphenols, for example in amounts of 0-5% by weight, especially 0.5-3% by weight alkylene oxidation product. The addition product of 8-11 moles of ethylene oxide and nonylphenol is preferred.

The new wood preservatives may also contain known drying substances (siccatives) (Rompp Chemie-Lexikon, 7th edition, volume 6, pp. 3692, 2693), for example in quantities of

0-3% by weight, especially 1-2% by weight. A mixture of the octoates of cobalt, manganese and lead is preferred.

The new wood preservatives can also contain known finely divided pigments (Rompp Chemie Lexikon, 7th edition, volume 4,

pp. 2693, 2694, 2695), for example organic or inorganic pigments, for example in amounts of 0-10% by weight, especially 2-5% by weight.

The new wood preservatives can also contain organic liquids, for example hydrocarbons or glycols, for example in amounts of 0-10% by weight, especially 6-8% by weight. A gasoline fraction with a boiling point of 180-220°C and butyl glycol is preferred.

In the production of the wood preservative according to the invention, it is for example possible to mix a 10% by weight aqueous solution of the oxidatively drying, acid-solubilized, low molecular weight 1,3-butadiene polymer which contains amino groups, and which at a pH value of 2-6 dissolve in water,

with 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine in 100% form without additional solvent or in the form of a 50% solution in an organic solvent. This creates completely homogeneous, clear to slightly cloudy mixtures. Even with a long storage time, such mixtures will not change, i.e. the active substance is not excreted from this mixture.

Surprisingly, such a mixture is able to absorb additional, known, per se water-insoluble, especially organic, biologically active substances. Thus, for example, it is possible to dissolve in this mixture those by protection of three common amounts of insecticides, for example hexachlorocyclohexane or 1-naphthyl-N-methylcarbamate, without using additional organic solvents.

Many other known active substances from the series of insecticides and fungicides with an effect against wood-destroying or wood-discoloring fungi which can be used for the protection of wood can also be used in the wood preservative according to the invention.

During application, the new wood preservative penetrates uniformly into the wood without causing the wood to swell. Thus, the disadvantages of the alkaline aqueous solutions are avoided.

Furthermore, it is important that the new wood preservative is non-flammable and very odorless. Depending on the concentration of the oxidatively drying, acid-solubilized, low molecular weight 1,3-butadiene polymer containing amino groups, which dissolves in water at a pH value of 2-6, in the wood preservative, impregnation primers are obtained with increasing concentration, open-pore wood protection glazes and dense-layer glazes.

The oxidatively drying, acid solubilized, low molecular weight 1,3-butadiene polymers containing amino groups,

and which are soluble in water at a pH value of 2-6, are normally dissolved in organic solvents. They can be used in solvent-free form or in the form of solutions for the production of the wood preservative according to the invention.

Depending on the form of delivery of the used oxidatively drying, acid-solubilized, low molecular weight 1,3-butadiene polymers containing amino groups, and which dissolve in water at a pH value of 2-6, the total content of organic solvents (preferably glycol derivatives) in the wood preservative at 3-10%.

For the experiments, an oxidative drying,

with acids solubilized, low molecular weight 1,3-butadiene polymer containing amino groups, which dissolves in water at a pH value of 2-6, which was prepared as follows.

Maleic anhydride is reacted with a liquid cis-poly-butadiene to an adduct, which is then reacted with an equivalent amount of N,N-dimethyl-1,3-propylenediamine. The reaction results in an unsaturated polymer containing juxtaposed N-(3-dimethylaminopropyl)-succinamide groups, which is designated as poly-(butadiene)-g-3-(1-(3-dimethylaminopropyl)-2,5-dioxo) -pyrrolidinyl. Such products are known from EP-B-9546.

The following examples of preparations will illustrate the composition of the wood preservative according to the invention. - 1) Wood protection primer, colorless, with preventive protection against wood-destroying fungi and insects. 7% oxidatively drying, acid solubilized, low molecular weight 1,3-butadiene polymer containing amino groups, which dissolves in water at a pH of 2-6 (BP),

1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

0.50% gamma-hexachlorocyclohexane

2% nonylphenyl + 8-11 mol ethylene oxide

84.50-81.50% water

3% butyl glycol

1.5-3% petrol fraction 80-220°C.

2) Wood protection glaze, pigmented, with preventive protection against wood-destroying fungi and insects.

20% BP

1-2% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

0.5 0% gamma-hexachlorocyclohexane

1% nonylphenyl + 8-11 mol ethylene oxide

2-5% pigment or pigment preparation

1-2% octoate of Co, Mn, Pb

68.50-62.50% water

1-2% petrol fraction 80-220°C

5% butyl glycol

3) Dense-layer glaze with preventive protection against wood-destroying fungi and insects.

28% BP

1- 2 2% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

0.50% gamma-hexachlorocyclohexane

1% nonylphenol + 8-11 mol ethylene oxide

2-5% pigment or pigment preparation

2% octoate of Co, Mn, Pb

52.50-47.50% water

12% butyl glycol

1-2% petrol fraction 80-220°C

4) Impregnating agent with a protective effect against wood-destroying fungi and insects, as well as against wood-discoloring fungi. 10% oxidatively drying, low molecular weight 1,3-butadiene polymer containing amino groups 4% 4-phenolsulfonic acid (for reaction with the amino groups) 2% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl- propyl]-cis-2,6-dimethylmorpholine

1% carbendazim (blue protection)

0.4 0% "Lindan" (gamma-hexachlorocyclohexane)

82.60% water

5) Impregnating agent against wood-destroying fungi.

5% oxidatively drying, low molecular weight 1,3-butadiene polymer

which contain amino groups

3% hydroboric acid

2% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

90% water

6) Primer with anti-blue effect

10% oxidatively drying, low molecular weight 1,3-butadiene polymer containing amino groups 4% araidosulfonic acid or boric acid (neutralizing agent) 2% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl ]-cis-2,6-dimethylmorpholine

1% carbendazim

83% water

7) Dip primer

8% oxidatively drying, low molecular weight 1,3-butadiene polymer

which contain amino groups

4% acetic acid

1% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine 1% "Furmecyclox"

0.5 0% TBTO

5% butyl glycol

1% wetting agent (adduct of nonylphenol + 8-11 mol ethylene oxide)

7 9.50% water

8) Dip primer 8.0 0% BP

4.00% acetic acid

1.00% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1.00% 1-[2-(2,4-dichlorophenyl)-1,3-dioxolon-2-yl-methyl]-1H-1,2,3-triazole ("Azaconazole")

0.50% TBTO

5.00% butyl glycol

1.0 0% wetting agent (adduct of nonylphenol + 8-11 mol ethylene oxide)

7 9.50% water

9) Dip primer 8.00% BP

4.00% acetic acid

1.00% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1.00% "Tridemorph"

0.5 0% TBTO

5.0 0% butyl glycol

1.0 0% wetting agent (adduct of nonylphenol + 8-11 mol ethylene oxide

7 9.50% water

10) Dip primer 8.00% BP

4.00% acetic acid

1.00% 4-[3-(4-(n)-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1.00% "Fenpropimorph"

0.50% TBTO

5.00% butyl glycol

1.00% humectant (adduct of nonylphenol + 8-11 mol ethylene oxide)

79.50% water

The following mixtures also illustrate the advantages associated with the mixtures according to the invention.

(A1) 7% BP

1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

2% adduct of nonylphenol + 8-11 mol ethylene oxide

3% butyl glycol

1.5% petrol fraction (boiling range 80-220°C) Water addition to 100%

(B1) 1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

2% adduct of nonylphenol + 8-11 mol ethylene oxide

3% butyl glycol

1.5% petrol fraction (boiling range 80-220°C) Water addition (pH value 2-6) to 100%

(C^) 7% BP

1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

2% adduct of nonylphenol + 8-11 mol ethyl oxide Water addition to 100%

(Dx) 1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

2% adduct of nonylphenol + 8-11 mol ethylene oxide Water addition (pH value 2-6) to 100%

(E1) 7% BP

1.5-3% 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

Water addition to 100%

(A2) 8% BP

1% 4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1% adduct of nonylphenol + 8-11 mol ethylene oxide

4% butyl glycol

1% petrol fraction (boiling range 80-220°C)

Water addition to 100%

(B2) 1% 4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1% adduct of nonylphenol + 8-11 mol ethylene oxide

4% butyl glycol

1% petrol fraction (boiling range 80-220°c)

Water addition (pH value 2-6) to 100%

(C2) 8% BP

1% 4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine 1% adduct of nonylphenol + 8-11 mol ethylene oxide Water addition to 100%

(D2) 1% 4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

1% adduct of nonylphenol + 8-11 mol ethylene oxide Water addition (pH value 2-6) to 100%

(E2) 8% BP

1% 4-[3-(4-(t)-butylphenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine

Water addition to 100%.

The testing of the mixtures shows that the mixtures A^, C-^, E-^, A2, C2 and E2 are clear aqueous stable solutions which do not change when stored for a long time. The mixtures are well suited as wood preservatives. The fungicidal active substances show their full fungicidal effect. The mixtures B^, D^, B2 and D2, on the other hand, are two-phase mixtures containing an aqueous phase and the solid active substance, which is deposited as a precipitate. These mixtures are unsuitable as wood preservatives, because the solid substance does not penetrate the wood, but remains in the form of a solid coating on the wood surface and falls off from it or is washed away by rain or blown away by wind.

The organosilicon active substances, for example 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine can be prepared as follows. The indicated parts are parts by weight.

10.0 parts of 2-methyl-3-(4-bromophenyl)-propyl chloride was added to 80 parts of THF (tetrahydrofuran). At -75 to -70°C

2.55 parts of n-butyllithium (dissolved in pentane) were then added dropwise, and after stirring for 30 minutes at -50°C, 6.6 parts of n-butyldimethylchlorosilane were added dropwise at this temperature. After stirring for 30 minutes at -50°C, the reaction mixture was warmed to room temperature and stirred for 12 hours.

After filtering and distilling off the solvent, the residue was distilled. At the boiling point 96-100°C/0.08 mbar, 9.8 parts of 2-methyl-3-(4-n-butyldimethylsilyl-phenyl)-22 were obtained

propyl chloride, nQ = 1.5033.

The propyl chloride thus obtained was reacted with cis-2,6-dimethylmorpholine corresponding to the following reaction.

13.5 parts of 2-methyl-3-(4-triethylsilylphenyl)-propyl chloride

and 16.5 parts of cis-2,6-dimethylmorpholine were mixed and stirred for 6 hours at 150°C. After cooling, the mixture was adjusted to pH = approx. 9 with saturated Na2CO^ solution. It was extracted with methylene chloride, the organic phase was dried and evaporated.

By distillation at 110-114°C/0.01 torr, 12.6 parts of 4-[3-(4-triethylsilylphenyl)-2-methylpropyl]-cis-2,6-

23

dimethylmorpholine, nQ = 1.5025.

The compound 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-

23

methyl-propyl]-cis-2,6-dimethylmorpholine has nD= 1.4950.

The wood preservatives according to the invention are used in the usual way, for example by applying, dipping or spraying the wood. They protect the treated wood effectively against destruction or discolouration by fungi or insects.

The amounts of the wood preservative used in the individual case depend on the content of active substance and are chosen so that the amount of wood preservative acting on the wood contains the amount of active substance that corresponds to the usual application amount of the active substance.

The aqueous wood preservatives according to the invention are produced, for example, by 3-50%, preferably 5-20%

of the 1,3-butadiene polymer in water, such an amount of acid is added that a pH value of 2-6, preferably 3-4, is achieved.

In this solution, to which small amounts of solvent and/or wetting agent (especially glycol derivatives and non-ionic ethylene oxide adducts) can be added to reduce the initial viscosity, they are effectively dissolved

some substances. Additional water is then added if necessary.

The preparations produced in this way are storage-stable and

are water-insoluble after application to the wood and oxidative drying.

The advantages of the agents according to the invention lie in the fact that they consist of only one phase, which counteracts separation of the active substances on the wood surface, and in the acidity regulation, which prevents swelling of the wood. The dissolved active substances can penetrate the wood without hindrance, so that with the help of these agents a better penetration depth and more extensive wood protection can be achieved than with conventional agents.

The absence of solvents, in whole or in part, enables safe and environmentally friendly use of the agents.

Attempt

Fungicidal effect against wood-destroying fungi after a

12-week vaporization treatment:

For testing the fungicidal effect against the wood-destroying fungi Coniophora puteana and Polystictus versicolor, according to DIN-Vorschrift 52 17 6, Blatt 1 "Priifung von Holzschutzmitteln, Mykologische Kurzpriifung (Klotzchen-verfahren)", pine goat wooden blocks (for Coniophora) and beech wood blocks (for Polystictus) with the dimensions 50 mm x 25 mm x 15 mm coated with the preparation mixture according to example 4 in an amount of .100 g/m 2 wooden surface. The test conditions were toughened by the wooden blocks being subjected to a 12-week evaporation treatment after 3 weeks of storage in a wind tunnel; below, the air temperature was 40°C + 2°C and the air flow speed 1 m/s + 0.1 m/s. The treated blocks were then placed together with the untreated ones in glass dishes containing as test fungi Coniophora puteana and Polystictus versicolor respectively on a nutrient agar. The bowls were then placed in a climate room at a temperature of 22°C and a relative humidity of 70%. After 3 months of experimental duration, the bricks were freed from adhering fungal mycelium and dried.

Then the degree of tree destruction was assessed - Evaluation core: 1 undamaged

2a in places a little attacked

2b overall little attack 3a in places heavily attacked 3b overall heavily attacked 4a in places completely destroyed 4b in general completely destroyed

The degree of fungal attack, as well as weight loss of the wooden blocks after

3 months trial and previous evaporation stress

When using the oily wood preservatives with 2% by weight of the active substance 4-{3-(4-(n)-butyl-dimethyl-silyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine (2 parts by weight of active substance were dissolved under slight heating in 55 parts of an aromatic gasoline fraction; then 10 parts of an alkyd resin were added and test gasoline filled to 100 parts at room temperature) poor results were obtained under the same test conditions as described above. This is due to poor penetration of the active substance:

Claims (3)

1. Aqueous wood preservative based on an aqueous solution of an oxidatively drying, acid-solubilized low molecular weight 1,3-butadiene polymer containing amino groups, characterized in that at a pH value of 2-6 it contains a water-insoluble active substance in dissolved form . 2. Agent according to claim 1, characterized in that it contains 4-[3-(4-(n)-butyl-dimethylsilyl-phenyl)-2-methyl-propyl]-cis-2,6-dimethylmorpholine as active substance. 3. Agent according to claim 1, characterized in that it contains 2-(methoxy-carbonylamino)-benzimidazole as active substance.