FI63514C - SAOSOM FUNGICID ANVAENDBAR HOMOGEN VAETSKEBLANDNING OCH FOERFARANDE FOER DESS FRAMSTAELLNING - Google Patents

Description

r * l ^ ANNOUNCEMENT. -, c „.

JBTa ** ^ UTLÄGGN I NQSSKKIFT 6 3514

JggJB C (45) Patent granted on 11 July 1933

ClS Patent oeddelat (51) Ky.lH.Vci.3 A 01 N 59/20 // A 01 N 37/02 FINLAND — FINLAND (21) 780531 (22) Hakemtopllvl — AmBknlngriag 17.02.78 (23) AikupUvt — Gtttlgh « sd »| i7.O2.78 (41) Tullut (ulklMlul - Blhrtt offantllg 18. 08.79 IWttl · J * r # ki * t * Rih * llltu * Nlhttvlk.lp.Km J. k „uLJulk *« n pvm.-

Patent · och r * gl «t * rftyr * l« * n 'Amaiun utUgd och uti. * Krtfun puMmntf 31.03.83 (32) (33) (31) Requested Utuelkeu * —Begird priorltet (71) BP Chemicals Limited, Britannic House, Moor Lane, London EC2Y 9BU,

England-England (GB) (72) David Berry, Hull, North Humberside, England-England (GB) (7 * 0 Oy Kolster Ab. (5U) Homogeneous liquid mixture for use as a fungicide and method for its preparation - for that purpose

The invention relates to a homogeneous liquid mixture for use with fungicides, comprising a copper-ammonium complex of one or more C 1 -C 4 monocarboxylic acids with 4 to 10% by weight of dissolved copper and water, and to a process for preparing such a mixture.

Copper salts have long been used as fungicides. In addition, the toxicity of soluble copper salts is also known. Although it is possible to prepare solid copper compounds of moderate and acceptable toxicity, the use of such solids, even in very fine form, is considerably limited due to the difficulty of spreading such solids evenly on the substrate surface to achieve maximum surface coverage for effective protection. towards. Even in cases where such copper compounds have been prepared in soluble form, these solutions have been very dilute solutions containing more than 60% by weight of solvent per n 8% effective copper content. Such mixtures of cuprammonium carboxylate are described in U.S. Pat. Nos. 3,900,504 and 4,020,180. they tend to precipitate and deposit in the containers used for transport. In commercial processes, such precipitation can also lead to blockages in the pumping and spraying equipment.

It has now been found that homogeneous aqueous solutions of cuprammonium complexes can be prepared which not only contain relatively smaller amounts of solvent but also have a higher effective copper content than has hitherto been produced.

The homogeneous liquid mixture according to the invention is characterized in that it contains up to 40% by weight of water and is prepared by reacting the acidic ammonium salt of a monocarboxylic acid with a copper compound which is copper oxide or copper oxide in the presence of aqueous ammonia.

The process according to the invention for preparing a homogeneous liquid mixture for use as a fungicide containing a copper-ammonium complex of one or more C 1 -C 4 monocarboxylic acids with 4 to 10% by weight of dissolved copper and up to 40% by weight of water is characterized in that the acidic ammonium salt of the monocarboxylic acid is reacted with a copper compound which is copper oxide or copper oxide in the presence of aqueous ammonia.

The monocarboxylic acid moieties of the salt may be derived from saturated or unsaturated monocarboxylic acids. Examples of such acids are formic acid, acetic acid, propionic acid. isomeric butyric acids, acrylic acid and methacrylic acid. By the phrase "acidic ammonium salt" is meant salts having two moles of acid moiety per mole of ammonium ion expressed as chemical equivalent. Thus, the ammonium salt of the acid is preferably ammonium diformate, ammonium diacetate and / or ammonium dipropionate. The product of the reaction between an acidic ammonium salt and copper oxide in the presence of aqueous ammonia is a dark blue aqueous solution containing a cuprammonium complex at a concentration within a defined range.

The liquid compositions of this invention have fungicidal activity due to the presence of copper. These mixtures therefore have several uses, for example as paint biocides, wood preservatives, fungicides to prevent mold on fabrics and to combat algae growth and ship fouling. In particular, these mixtures inhibit the growth of fungi such as Cladosporium Herbarum, which causes paint spoilage, and Coniophora cerebella, which causes the decay of wood 3 6 3 51 4.

For all the above purposes, the mixtures can be used as such as aqueous solutions. However, the aqueous solution may contain other conventional additives capable of supplementing their activity, such as free formic acid, propionic acid, formalin and bisulfites. Aqueous solutions may also contain wetting, spreading or adhesive agents or may be emulsified with mineral oils, if necessary.

The concentration of the cuprammonium complex applied to the substrate depends not only on the substrate and its end use, but also on the nature of the effect to be treated or prevented. However, those skilled in the art can easily find out. For example, an amount of treatment corresponding to copper concentrations between 0.4 and 1.0% can be used for wood protection.

When it is desired to dilute the cuprammonium complex solution for use in a large volume, such as in the above-mentioned wood preservative, it is preferable to dilute using 1.3% aqueous ammonia solution to prevent precipitation of the complex. If water alone is used as a diluent, for example at dilutions of about 100: 1, a flocculant gelled blue precipitate may separate.

The cuprammonium complexes of this invention have a higher solubility in water than conventional copper salts such as copper formate and copper propionate and, when prepared into solutions, have a pH between 7-9. Their better solubility allows the mixture to flow more freely and spread more evenly on the substrate, especially when used as sprays. As can be seen from the table, the copper-ammonium complexes are more soluble in water than copper-propionate and copper-formate, which facilitates spray application. The differences in copper solubility (at ambient temperature) are shown in the following table:

Table 1 - -- ·- ....... ....- ----------- .

Compound% Cu in saturated aqueous solution

Copper propionate 2.2

Coprammonium propionate complex 5-10.0

Copper formate 2.9

Copperxnonium formate complex 4.5

_ _ I

The invention is described in more detail in the following examples.

Examples A. Preparation of complexes

The complex can be prepared by reacting an acidic ammonium salt (70% by weight aqueous solution) with either copper or copper oxide and aqueous ammonia. Some manufacturing methods are described below.

Copperammonium propionate complex 1. A 70% aqueous solution of ammonium dipropionate (212 g) was added to cupric oxide (30 g) and the mixture was refluxed for 30 minutes. After cooling, 88 g of aqueous ammonia (33.3 wt% NH 4) were added and the mixture was filtered to give a dark blue solution containing 13.5 wt% NH 4, 39.8 wt% propionate, 7.0 wt% -% copper and 39.7% by weight water (pH = 8.0).

2. A 70% aqueous solution of ammonium dipropionate (106 g) was added to cupric oxide (30 g) and the mixture was refluxed for 30 minutes. After cooling, 44 g of aqueous ammonia solution (33.3% by weight NH 4) were added, the solution was re-cooled and filtered to remove unreacted copper oxide (6.6 g). The final solution contained 13.0 wt% NH 4, 38.2 wt% propionate, 10 wt% copper and 38.8 wt% water (pH = 8.0).

3. A 70% aqueous solution of ammonium dipropionate (212 g) was added to cupro oxide (30 g) and the mixture was refluxed for one hour. After cooling, 88 g of aqueous ammonia solution was added, · (3> 73% by weight), the solution was cooled and filtered to remove excess copper metal (12 g). The final solution 5 4 3 51 4 contained 14.0 wt% NH 4, 41.3 wt% propionate, 5.0 wt% copper and 39.7 wt% water (pH = 7.6).

Copperammonium formate complex 4. This complex was prepared by reacting cupric oxide with aqueous ammonia and 70% aqueous ammonium diformate. The final solution contained 4.5% by weight of copper, 40% by weight of formate and 39.0% by weight of water.

B. Activity of cuprammonium complexes

Wood Preservative Activity 5. The complex at various dilutions in the solution was run on pine wood pieces of Pinus sylvestris as follows: The pieces were dried in an oven and saturated in vacuo with a solution of cupr ammonium propionate. Twelve (12) bodies were treated with each of the following complex concentrations in solution, expressed as copper: 1.0, 0.63, 0.40, 0.25, 0.16, 0.10, and 0.063%. The pieces treated in this way, together with the untreated pieces, were exposed to a culture of Coniphora cerebella in bottles containing mold for six (6) weeks.

After this time, the specimens were removed from the culture, weighed, oven dried and reweighed. The final oven-dry pulp was compared to the original dry pulp to calculate the weight loss due to the disintegration caused by the organism. Two pieces, treated at each concentration and not exposed to the organism, were also dried in an oven and weighed to correct for the effect of absorption of the preservative complex.

Based on weight loss, the toxic limit, i.e. the difference between the concentration that just allows decomposition and the next concentration in the series that prevents all decomposition was 0.25-0.40% copper in the treatment solution. The concentration in the wood, expressed as 3 copper, was 1.9 to 3.2 kg / cm of wood for this toxic limit.

For further comparison, one of the most commonly used aqueous preservatives, based on copper sulfate, potassium dichromate and arsenic pentoxide and known as the "CCA preservative", was tested as described above using pieces of the same wood and the same organism. This gave a toxicity limit of 1.8 to 3 3.0 kg / cm expressed as metal content. Thus, with a metal content similar to CCA, the present invention allows the use of 6351 4 more acceptable copper corlexes.

Activity of paint bleach 6 * The activity of copper ammonium propionate as a paint biocide was determined as follows:

Copper ammonium propionate (500 ppm) was added to a molten medium (50 ° C) consisting of Czapek Dox agar (Oxid CM 97) and this was poured into 100 mm Petri dishes and the mixture was allowed to cure. Surface moisture was removed from the growth medium by drying at 50 ° C. Agar plates were seeded with suspensions of test organisms using a multipoint implant and germinated for seven (7) days at 25 ° C. The corresponding reference medium to which no complex was added was prepared, seeded and germinated under similar conditions. The following spore germination results were obtained. In all cases, even the slightest growth or germination of spores was considered to be part of the failure of the preservative to inhibit the growth of organisms.

* i

Compound Test organisms

Cladosporium Fusarium Penicillium Pestalotia Herbarum species expansum macrotricha

Coprammonium- no germination no germination- no germination no germination propionate from (500 ppm)

Comparison Positive Positive- Positive Positive germination vinen germination germination germination

Claims (3)

6351 4 7 A homogeneous liquid mixture for use as a fungicide, comprising a copper-ammonium complex of one or more C 1 -C 4 monocarboxylic acids with 4 to 10% by weight of dissolved copper and water, characterized in that it contains not more than 40% by weight of water, and that it is prepared by reacting the acidic ammonium salt of a monocarboxylic acid with a copper compound which is copper oxide or copper oxide in the presence of an aqueous ammonia solution. A process for preparing a homogeneous liquid mixture for use as a fungicide, comprising a copper-ammonium complex of one or more C 1 -C 4 monocarboxylic acids with 4 to 10% by weight of dissolved copper and up to 40% by weight of water, characterized in that the acidic ammonium salt of the monocarboxylic acid is reacted with a copper compound which is copper oxide or copper oxide in the presence of aqueous ammonia. Process according to Claim 2, characterized in that the ammonium salt is ammonium diformate, ammonium diacetate or ammonium dipropionate.