DE2506431A1 - ALGICIDES AND WATER HERBICIDES - Google Patents

Description

SANDOZ-PATEOT-GMBH. Dr. y. Γ- .. · ^! -; '; w-ra! c Case 630-6670

785Ο Lörrach Tues / Lf.; ». ^{r 1} ^

Dr. Γ. '■:. -.-.dm

$ Frcfa.fi »; . '.'., Gr. tsci.aiineitnec StS.38

Algicides and water herbicides

The present invention relates to copper complexes, in particular the use of copper (II) complexes as algicides and water herbicides.

The present invention relates to a method for controlling algae and / or aquatic weeds in the waters infested with it, characterized in that an effective amount of the complex from one to the Complex formation capable copper (II) compound and an amine of the formula I,

r * R. ~ η N \ R. 3 , 2 - NO - ^R 4

wherein R, R, R and R independently of one another are hydrogen or an alkyl radical with 1 to 3 carbon atoms,
R_ is a straight-chain or branched alkylene group

with 2 to 6 carbon atoms and η is a number from 1 to 5,

or an aminoalkylene-alkanolamine ,.

wherein the alkylene chain contains 2 to 5 carbon atoms and the alkanol radical contains 2 to 5 carbon atoms, with * provided that aminoalkylene-alkanolamines only used together with copper (II) salts in the complex and only to control aquatic weeds should be

used.

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If η is greater than 1, the repeating Units R may be the same or different among themselves.

In general, copper (II) compounds capable of complex formation are those copper (II) compounds from which a tangible amount of copper (II) ions is formed in an aqueous medium. Examples of such groups capable of complexing copper II compounds include cupric hydroxide (also known as cupric oxide hydrate), copper-II-salts of inorganic acids such as copper-II-sulphate _f cupric carbonate, copper II-nitrate, copper-II-chloride, copper-II-bromide, copper-II-chlorate and copper-II-suifamat [Cu (SO3NH ₃ J ₂ ] and of organic acids like carboxylic acids including mono- and polycarboxylic acids as well as amino acids like eg Copper (II) formate, copper (II) acetate, copper (II) citrate, copper (II) tartrate, copper (II) benzoate, copper (II) gluconate, ie simple copper salts of inorganic and organic acids (in English as "acid copper salts "), and double salts with copper (II) hydroxide, generally referred to as basic copper (II) salts, such as basic copper carbonate [Cu (OH)« CuCO], basic copper chloride [Cu (OH) «CuCl_] and basic copper sulphate [Cu (OH) ₂ 'CuSO.]. Of particular interest are the complexes derived from copper (II) hydroxide, which are also known Finally acidified with preferably one equivalent of acid, and especially the complex compounds derived from copper (II) sulfate, for example the complexes derived from copper (II) sulfate pentahydrate. In the process according to the invention, preference is given to using copper (II) complexes - formed from "acid copper (II) salts" - as copper (II) compounds capable of complex formation.

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According to the technology, such complexes can also be made from copper (II) hydroxide or a basic copper (II) salt can be obtained by adding the resulting basic copper (II) salt complexes in a further process step acidified with at least one equivalent of an acid, for example a mineral acid.

The amino alkylene alkanolamines preferably used for complex formation are those in which the alkylene radical has 2 to 3 carbon atoms and the alkanol radical has 2 to 3 carbon atoms Has carbon atoms; the use of aminoethylene-ethanolamine is particularly preferred.

The amines according to formula I which are capable of complex formation include alkylenediamines such as ethylenediamine, 1,2- or 1,3-propylenediamine, N-methyl-ethylenediamine, N, N ¹ -dimethyl-1,3-propylenediamine, N-methyl 1,3-propylenediamine, N-methyl-1,3-propylenediamine and N, N, N ¹ , N'-tetraethylene diamine and polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine and dipropylene triamine.

When R or R or R or R in formula I is alkyl stands, this is preferably understood to mean methyl or ethyl, especially methyl.

Preferably at least one, but preferably two or three radicals, in particular all of the radicals R. to R., are hydrogen. Furthermore, R ₅ in formula I preferably contains two to five, particularly preferably 2-4, for example 2, 3 or 4, very particularly 2 carbon atoms. R_ preferably represents a straight-chain unit, for example of the formula - (CH) -, where m is 2 to 6.

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In formula I, η is preferably a number from 1 to 4, in particular from 1 to 3, _f such as 1 or 2, in particular 1.

A group of amines especially used for complex formation come into question, thus represent the compounds of formula Ia,

-f N -

· ^Ε 3

N Ia

where R ', R', R 'and R' independently of one another are water

J- £ * »5 ^ z

mean substance or methyl

and R 'is an alkylene radical having 2 to 4 carbon atoms

and n ^{1 is} a number from 1 to 4.

The amines of the formula Ib are particularly preferred as complex-forming groups

R '- N - R' - N Ib

⁵ \, ^R 4

wherein R ^, R ^, R ^, R 'and R ^ have the meanings given above,
and in particular the amines of formula Ic

H ₂ N - R ^ - NH ₂ ic

wherein R 'has the meanings given above; ethylenediamine should be mentioned in particular. The totality the amines of the formula I and the aminoalkylene-alkanol

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amines which, according to the definition above, for complex formation can be used are hereinafter referred to briefly as "amines".

It should be noted that any mixture of amines was used to make the complexes can be, resulting in a mixture of complexes or complexes with mixed ligands or both. In addition, mixtures of Cu (II) salts capable of complex formation can also be used. One Copper (II) complex compound as defined above of the invention is hereinafter referred to as "complex" for short.

The complexes of the invention can be conveniently prepared by reacting the copper compounds in an aqueous medium done with the amines.

Since the reaction generally exhibits an exothermic heat release, it is expediently allowed to proceed without the supply of heat, the addition of the reactants being such that the reaction temperature remains ^{below 70 ° C., for example.} The preferred stoichiometric ratio of the reactants is in the range 1-10 moles of amine per 1 g atom of eggs. Copper (calculated from the Cu-II compound), preferably 1-5 moles of amine to 1 g-atom of copper, particularly preferably 1-3 moles of amine to 1 g-atom of copper. Especially the complex of 2 moles of amine to 1 g-atom eggs. Copper is most preferred from the practical point of view.

Thus one observes with the complex, which with one reactant- ratio of 2 moles of ethylenediamine to 1 g-atom eggs. Copper is formed, very useful stability ratios (log K value of 20.03, K = dissociation constant of the com-

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plexes). The complex can be represented by the structural formula

[Cu (H ₂ N-CH ₂ -CH ₂ -NH _{2) 2} (H ₂ O) _2] ²⁺ X

where A is an anion and

χ and y stand for 1 or 2, with the proviso that

the product of χ and y 2 should be reproduced.

The copper (II) complexes can according to the invention after a the usual application methods can be used, e.g. by spraying or scattering on the water surface. Another method of application that can be used is by means of a trailing hose technique.

The complexes can per se, i.e. in solid form, for example by sprinkling, or simply dissolved in water or are used in formulations, the formulations being those customary for herbicides or algicides Can contain carrier materials, diluents and, if appropriate, adjuvants.

The formulations can be solid or liquid, e.g. In the form of solid preparations, for the controlled release of the active ingredient (slow release pellets) or in concentrated form , aqueous solution or in concentrated emulsions. Examples of carriers or diluents are talc, Starch, gelatin, xylene, diesel oil. The formulations can also contain surface-active substances, e.g. the emulsifiers Aliquat ^ C Brand Name, Product of General Mills, Inc., Chemical Div, / Illinois, USA, the coconut trimethylammonium chloride contains), Spra-mate® (brand name, product of the company. KDM Company, San Antonio, Texas, USA, which manufactures the acid

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contains salt of a fatty amine) and S-120 Ό (brand name., Standard Spray & Chemical Company, Lakeland, Florida, USA). The emulsifiers, in particular Cationic and non-ionic emulsifiers such as Spra-mate or S-120 can be used together with an organic Phase, e.g. xylene or diesel oil, can be used to form a "water-in-oil" invert phase.

In general, it is not necessary to isolate the complex from the reaction mixture in which it was formed. Thus, the resulting reaction mixture itself, optionally after lowering the pH, for example by adding dilute mineral acid, can be used as an algicidal or herbicidal agent - as desired also together with carrier materials, diluents and / or adjuvants.

The copper content of the solutions or formulations of the Complex is preferably in the range of 1-12% by weight, especially 6-10, especially 7-8.5, e.g. 8% by weight.

The pH. of the complex in the form of aqueous preparations preferably in the range from 6 to 12, especially 7 to 12, for example 8 to 12, especially in the range 9 to 11.5, e.g. at 10.

The complexes are preferably applied in such a way that in the water into which they are applied, mathematically one A concentration of 0.1-10 ppm, particularly preferably 0.3-6 ppm, especially 0.5-1.0 ppm, of elemental copper is formed.

The complexes can also be used as a mixture with other herbicides or algicides. As an example of in question

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Upcoming additional active ingredients are Ammate ^w (brand name, inorganic ammonium sulfamate herbicide, a product of EI Du Pont de Nemours & Co., USA), Deiguat (common name, an organic herbicide, product of ICI Ltd., Great Britain, the l, l'- Contains ethylene-2,2 ^l -bis (pyridinium) dibromide as active ingredient), salts of the endothal (common name, organic herbicide, product of the company Penwalt Corp., USA, the 3,6-endo-oxo-hexahydrophthalic acid. As active ingredient contains) such as Aguathol-K ® (brand name, organic herbicide, product of Penwalt Corp., USA, which contains the dipotassium salt of 3,6-endo-oxo-hexahydrophthalic acid as an active ingredient

contains) or K-Lox (brand name, a copper complex, formed from copper hydroxide and triethanolamine with herbicidal / algicidal effect, product from Sandoz AG, Switzerland).

According to the invention, the complexes are suitable for combating many forms of algae - including thread algae - of the order Cladophora and Spirogyra, living planktonically Algae such as Microcystis and Anabaena, algae found in swimming pools, commonly known as black, brown and red algae are known, and algae living in ponds and lakes such as Dictyosphaerium, Oedogonium, Chlorococcum, Pithophora, Hydrodictyon and Lyngbya.

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In addition, the complexes are suitable according to the invention for Control many types of aquatic weeds, including the Najadaceen, Vallisneriae, Hydrillae, Myriophyllum verticillatum, the hyacinths and Egeria, especially Hydrilla verticillata and Egeria densa. The method of the present invention is preferably directed primarily on combating aquatic weeds.

An advantage of the complexes according to the present invention is also their very low fish toxicity, as in the example of toxicity [LC = that concentration at of which 50% of the fish population are killed] a copper (II) sulfate pentahydrate / ethylenediamine (1: 2) complex for Lepomis macrochirus (species: sunfish) was detected after 24 or hours. They are therefore very good for Waters with fish stock suitable.

In addition, the complexes have no inadmissible high corrosiveness and also show no particular tendency to Deposition of elemental copper, as from the sub Investigations into the corrosion of aluminum and mild steel emerged. They are therefore also suitable for use there in water, where contact with machine parts such as pumps and pipes is to be expected.

The complexes are remarkably stable even under conditions such as a pH between 6 and 12 and especially under basic conditions Conditions. Therefore they are suitable for use in alkaline waters, e.g. with a pH between 7 and 11.

""HM.,

8 /: 10Ό2

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The following examples serve to illustrate the invention. Percentages relate to percentages by weight. The temperatures are given in degrees Celsius. Specific density and viscosity are determined at 25 ° C. The viscosity data are given in centipoise units (cP).
B ei sp .i. .e .1.1

1 mole of copper (II) sulfate pentahydrate (CSP), crystalline, becomes with 2 moles of 91-93% ethylenediamine EDA ("reagent grade "; remainder: water). The reaction is strongly exothermic. The copper (II) sulfate pentahydrate is added in portions over 1/2 hour so that the temperature remains below 70 °. The dark purple one The solution is diluted with water to such an extent that the result is a copper content (based on eggs. Copper) of 7%. The resulting solution has the following physical properties: pH = 11.5, specific density = 1.182 at 25 ° .. viscosity 13.6 cP at 25 °.

At. s p. i. e. 1

^a ) ίϊϊ-solution

567 It of water and 187.8 kg of 99% ethylenediamine (EDA) are placed in a Cowles dissolver. The temperature of the well-stirred solution is 56 °. While stirring, 181.4 kg of copper (II) sulfate pentahydrate (CSP) crystalline (specification: 100% permeability for 30 mesh, 95% non-permeability for 100 mesh sieve) are added over the course of 5 minutes. The temperature rises to 68 °. It is still CSP-crystalline 45 kg-wise in half-hour intervals to are inserted kg up to a total 390th A molar ratio EDAiCu of 1.998: 1 is calculated based on a copper equivalent ¥ ie_ ¥ PP * JtSa) P * ^for crystalline

ORIGINAL fNSPECTED

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CSP. The pH of the solution is 8.0. After the addition of 100 It of water and 5 kg of 99% ED and more After stirring for 15 minutes, the pH is 10.6. The copper content is 8.12%, the specific gravity at 25 ° is 1.224. A total of 908 It product will be in 5 gallon containers packed up. An overview of the analytical and physical properties of the solution of the The following list provides complex information:

Analysis: Found: Calculated : Cu 8.12% 8.00% EDA 15.24% H ₂ O 64.67% C. 6.48% 6.05% H 9.32% 9.28% N 7.31% 7.05% so ₄ 11.13% ^ß) 12.08% pH 10.6 - Density (25 °) 1.224 g / cm ³ - Viscosity (25 °) 14.5 cP colour Dark purple

α) based on the aqueous solution with 8% metallic Copper and a molar ratio of amine to copper of 2: 1

ß) based on a total sulfur content of 3.71%

The pH of the resulting solution can be brought to 10, for example, for the purpose of use as a water herbicide or algicide, for example by adding mineral acid.

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From the solution of the complex, crystals of bis (ethylenediamine) copper (II) sulfate can be precipitated in 100% yield by adding five times the volume of 95% alcohol. The crystals are separated off by filtration. The filtrate was colorless and practically free of copper. The product is dried overnight at 30 ° in a vacuum oven.

The analytical values for Cu, S, C, H and N (compare the following table) confirm the formula Cu (EDA) SO.

% calculated for % found 2 2 2 2 2 ' 22.78 22.6 34.33 34.5 °° 17.3 16.95 5.77 5.89 20.2 19.96

α) Calculated on the basis of the found sulfur value of 11.5%

A significant control of the water weed Hydrilla when applied in ponds was achieved with this material at a Cu concentration in the water of no more than 0.5 ppm.

Eg p. i e. 1st . 3

To a solution of 133 g of anhydrous EDA (98%) in 273 ml of water , 117 g of copper ( II) hydroxide are slowly added with stirring, the copper hydroxide rapidly dissolving . The addition is set up in such a way that the temperature remains below 50 °. After the solid is completely dissolved,

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are added to 273 ml of water. The resulting solution has a bluish purple color compared to the dark purple color of the copper sulfate product (Example 2). After cooling to 25 ° with continued stirring, the following data are found for the solution: 8.1% Cu, pH approx. 14, density 1.138 (at 25 °) and viscosity 12 cP (at 25 °). To improve the stability of the solution, the pH is brought to a value between 11 and 11 by adding a mineral acid, for example sulfuric acid, in at least an equimolar amount.
B is ρ ie 1 4

In analogy to Example 3, 102 g of copper (II) hydroxide are used (1 g atom Cu) to 145 ml 91-93% ethylenediamine (2 molar to EDA) in 561 ml of water. The hydroxide goes into solution quickly as long as you get it to the original level heated EDA solution there. However, the temperature then falls and the mixture is stirred at 30 ° for 4 hours until complete dissolution. Finally, you get a deep blue solution. The solution has the following Properties: 8.15% Cu, pH approx. 14, density 1.136 (at 25 °), viscosity 14.5 cps (at 25 °).

To improve the stability of the solution, the pH of the solution is adjusted to a value by adding mineral acid brought between 9 and 11.

B e i s. Ρ i e .1

In an analogous manner to that described in Example 1, can one 131 g of CSP 'slowly with 82 g of 90% 1,2-propylenediamine react in aqueous solution. The temperature of the batch rises to 69 °. Diluted after an hour one with water until a copper content of 8.01% is reached. Further properties of the solution are: pH = 10.7,

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Density 1.22 (at 25 °) j Viscosity 20 _C P (at 25 °).

The corresponding Cu complexes with diethylenetetramine, triethylenetetramine, 1,3-propylenediamine, N, N ¹ -dimethy! Propylenediamine, N-methy1-1,3-propylenediamine and tetraethylenepentamine and .Aminoäthylen-ethanolamine can starting from copper (II) sulfate and / or copper (II) hydroxide can be prepared in an analogous manner. If copper (II) hydroxide and aminoethylene-ethanolamine are used, the process step of acidifying with a mineral acid, for example sulfuric acid, in at least an equimolar amount is added.

B. e. i. s p. i. · e. .1. . 6th

Analogously to Example 5, 5.131 g of CSP are added to an aqueous one Solution containing 96.2 g of N-methylethylenediamine. After 8- - Hours of stirring and dilution of the solution until a copper content of 8.09% is reached, the following properties are achieved the solution found: pH = 11.9; Density 1.215 (at 25 °); Viscosity 24 cP (at 25 °).

Solutions with a copper content of 8% are prepared using ethylenediamine / copper in a molar ratio of 2: 1 starting from copper (II) chloride [CuCl ₂ -2H ₃ O copper (II) acetate [Cu (CH ₃ CO ₂ ) ₂ · H ₃ O], copper-II-nitrate [Cu (NO-) _o · 3H_O] and copper-II-sulfamate [Cu (SO NHJ J-

Solutions.

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B. e .1 s ρ i e 1

The complex in the form of its solution according to Example 2, part a), at which the pH has been brought to 10, is in 3 water fields (each with approx. 8.1 ar area and approx. 150 cm Depth) that are infested with aquatic weeds, including the water hyacinth, and with algae. The solutions were formulated as follows:

Field 1 - 60.6 It complex solution

227 It water

11.35 It Spra- mate
and 56.8 It xylene

Field 2 - 30.3 It complex solution

15.1 It Aquathol-K (40.3% active ingredient) 227 It water
11.35 It Spra- mate
56.8 It xylene

Field 3 - 30.3 It complex solution

15.1 It Diquat (36% active) 238.4 It water
11.35 It Spra- mate
56.8 It xylene:

The individual preparations are applied in the spray process in such an amount that a copper content of 0.5, 0.25 or 0.25 ppm (based on elemental Copper) in fields 1, 2 and 3 respectively.

In all cases 5 weeks after spray application achieved significant herbicidal and algicidal effects.

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B e 1 s ρ i e 1 8

The complex in dissolved form according to Example 2, part a) (after the pH has been brought to 10.0) is in 3 water fields with water weeds (including water hyacinths and Hydrilla). The following solutions were applied:

Field 1 (4.05 ar) 60.8 It complex solution with a

Eggs concentration of 1 ppm. Copper related to "acre foot"

Field 2 - strips of 2.7 mx 122 m

15.14 It complex solution

7.57 It Diquat (36% active ingredient) 11.34 kg of Ämmate

and 1.89 It S-120 dispersed in one

organic diesel oil phase for inverse treatment, with a resulting Copper concentration of 0.25 ppm per "acre foot"

The inverse treatment was carried out using hoses that are moved along the bottom of the water.

In all cases there was a significant herbicidal effect.

B e i s ρ i el 9

Various complexes have been tested in laboratory studies against the aquatic weed species Hydrilla verticillata. the Complexes on their own or in a mixture with other herbicides

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were applied in aqueous solution so that the following Concentrations of elemental copper resulted:

Solution SHPf ^ iS ^^^ it-lEEifl

CuSO · 2- ^ ethylenediamine) - ° r ⁵

complex

CuSO. 2- (N-Methy1-ethylene- 0 _f 5

diamine) complex

CuSO ₄ * 2- (I ₁ , 2-propylenediamine) - 0f5 complex

CuSO ₄ * 2- (1 ^ - propylenediamine) - .0.5 complex

CuSO * tetraethylene pentamine-0.5

complex

mixture

CuSO. · 2- (ethylenediamine) 50% ί

I 0.5

Cu (OH) * 2- (triethanolamine) 50% J

Cu (OH) 2- (ethylene diamine) complex 0.5 CuSO ₄ 2- (aminoethylene ethanolamine) complex 0.5

The evaluation was made 2 and 4 weeks after treatment, respectively performed. A herbicidal effect was observed in all cases, especially after 4 weeks.

The CuSO. · 2- (Ethylenediamine) complex was analogous Also used against the aquatic weed species Egeria densa. A herbicidal effect is also observed here.

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Example 10

The complex solution according to Example 2, part a) with a pH of .10 was tested in laboratory tests against the algae Microcystis aeraginosa, Lyngbya versicolor and Pithophora at a copper concentration between 0.01 and 1 _r 0 ppm based on elemental copper. An algicidal effect was observed in all cases, at least at the highest concentration.

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Claims (8)

- 19 - 630-6670 P a .t e η. .t a. n. s p. return ΠΛ Methods of combating algae and / or Aquatic weeds, characterized in that an effective amount of the complex is used for complex formation capable copper (II) compound and an amine of the formula I Ϊ2 K-R wherein R- / R ₂ , R and R. independently of one another are hydrogen or an alkyl radical with 1 to 3 carbon atoms, R_ is a straight-chain or branched alkylene group with 2 to 6 carbon atoms and η is a number from 1 to 5, or an aminoalkylene alkanolamine, where the alkylene chain contains 2 to 5 carbon atoms and the alkanol radical contains 2 to 5 carbon atoms, with the proviso that aminoalkylene-alkanolamines should only be used together with copper (II) salts in a complex and only for combating aquatic weeds,
used as an active ingredient. 509838/1002 - 20 - 630-6670 2. The method according to claim 1, characterized in that the capable of complex formation Copper (II) compound copper (II) hydroxide, copper (II) sulfate, Copper-II-nitrate, copper-II-chloride, = - Copper (II) bromide, copper (II) chlorate, copper (II) sulfamate, Copper (II) formate, copper (II) acetate, copper (II) citrate, Copper (II) tartrate, copper (II) benzoate, copper (II) gluconate, basic copper (II) carbonate, basic copper (II) chloride or basic copper (II) sulfate. 3. The method according to claim 1, characterized in that that the complex contains the elements of a copper (II) salt. 4. The method according to claim 1, characterized in that the amine of the formula I is ethylenediamine is used. 5. The method according to claim 1, characterized in that the ratio of the amine of the formula I for elemental copper 1 to 10 moles of Amih per 1 g atom Copper, preferably 1 to 5 moles of amine per 1 g atom of copper, in particular 1 to 3 moles of amine per 1 g atom of copper, especially 2 moles of amine per 1 g atom of copper. 6. The method according to claim 1, characterized in that the complex in dissolved and / or in emulsified form in a concentration that contains 1 to 12% by weight of elemental copper, preferably 6-10% by weight, in particular 7-8.5% by weight of elemental copper is used. 509838/1002 - 21 - 630-6670 7. The method according to claim 1, characterized in that the treated after application Water contains a copper content of 0.3 to 6 ppm, preferably 0.5 to 1 ppm, based on elemental copper. 8. Agent for combating algae and / or aquatic weeds, characterized by a content of one or more copper (II) complex compounds according to claim 1 as the active component. 3700 / HT / GM 5ü 9838/1002