FIGHT AGAINST ALGAE AND WATER WEEDS

The invention concerns the use of copper H Komplexverbindungen, those zweiOHeLiganden at least and at least one Alkanolamin ligand of the general formula whereby RI for a hydroxyalkyl remainder with 2 to 10 carbon atoms stands and R2 and R3 independent from each other for hydrogen, eineaAlkylrest with 1 to 8 carbon atoms, a Hydroxya [kylrest with 2 to 8 carbon atoms or a Aminoalkylrest with 1 to 8 carbon flavours stands, whereby the total carbon number of the remainders is to amount to g 1, R2 and R 2 to 10, contained in l of oordlnativer allocation to a copper ii-ion, to the fight against algae and water weeds. Characteristically of the copper ii-complex connections, which are used erfindnngsgemäß, their considerable water solubility is, even under basic conditions. According to invention used the complex connections manufactured by Komplexlerung, i.e. through conversion of copper ii-hydroxide (copper H oxydhydrat inclusively) and/or copper ii-hydroxide connections narrow-holding, in particular Doppalsalzen of copper ii-hydroxide, which are usually called basic copper H salts, like e.g. basic copper ii-chloride (also under the designation Eupfer [...] oxychlorid admits), that the formula approx. (OI2. CuCI2 corresponds, basic copper [...] sulfaL, according to that formula cu (WHETHER) to 2 “CuSO4 'or basic copper carbonate, which the formula cu (OI]) 2nd CuCO corresponds, with a Alkanolamin of the general formula indicated above (1). Beispisle for suitable mono, Dlund Trialkano [amines are mono ethanol amine, Diä hanolamin, tri ethanol amine, Dimethyläthanolamin, Diäthyläthauolamin, amine OAU hyläthanolamin, mono isopropanol amine, Diisopropanolamin, Triisopropannlamin and ME hyldiäbhanolamin and mixtures of these connections. Preferential Alkanolamin is Triä hanolamin, in particular as a main component of a eahnischen Diäthanolamin/Triä hanolaTn --Gemisehes, i.e. in a relationship of 16: 85 Gew. - Parts. Preferably copper ii-hydroxide or a basic copper H salt, particularly however the first, is used for the Komplexbildung. DieKomplexblldungsreal; ion can be accomplished for example in such a way that the copper ii-connection to an aqueous solution, preferably, is given to a concentrated password of the Alkanolamins. The reaction will at a pH of at least 8, accomplished 5, preferably in a pH range of 8, 5 to 13, 0 under special preference of the pH range from 9 to 12, particularly the pH range 9 to if necessarily, can the basicity of the solution by addition of a suitable acid, for example a Miueralsäure such as sulfuric acid, be lowered. The Reak of ion emperatur lies preferably within the range of 20 to 80oc, particularly preferentially in the range 30 to 60oc. Since the reaction runs usually easily exothermically, should be paid attention during the execution of the reaction in the above-mentioned Tempera urbereichen if necessary to the necessary cooling. The function duration is the material union between 20 min and 6 h is accomplished not critically, generally. The molar ratio from Alkanolamin to copper H connection can vary naturally. Generally it is to be preferred however, with a molecular surplus of Alkanolamin to arbe EN. The processing of the Reak iousansa zes with the goal of the isolation of the formed complex connection can be made in the usual way. For example the formed complex connection can, since it is water soluble much gu, but in many organic solvents, by Ausf'ällung by means of addition of a suitable, mi water of misehbaren solvent is insoluble in the surplus, the double ReakLionsvolumens, a solvent as for example acetone to be e.g. isolated. For dispatch, Aufbewahrungsund Applika ionszweeke one uses the complexes verzugsweise in form of concentrated solutions (concentrate), e.g. in more aqueous or in more alcoholically (methanol to hexadecimalget) solution, preferably does to aqueous medium. To the production of a preferential form of the concentrate will the formed Komplex'verbindung, without isolating, leave in the material ionsmedinm it. Any solids in the material ion medium favourable-proves removed, e.g. by field ration and/or Zen rifugation, with the result, there a clear, concentrated solution develops. If one uses the Reaktionsgemiseh as concentrate of the Komple.xverbindung, one sets the material anten in one confines limited molar ratio into the reaction with the goal of avoiding inappropriate concentrations at one of the two reaction partners in the concentrate. Therefore the molar ratio Alkanolamin lies in the available case: Copper H connection preferably within the range 1, 75 to 2, 2: 1, favourably within the range 1,9: 2, 1st 1, particularly 2: 1. One continues to strive a END pH value of the material of ion medium within the range 8, 5 to 11, particularly prefers 9, 2 to 9, 6 on. It found that the above-mentioned copper H Komplexverbindungen is in water remarkably solubly and stable, particularly within the basic range. Consequently concentrated solutions with a content between 1 and 11 Gew can. - %, preferably 6 to 10 thread - %, in particular 7 to 9, 5 Gew. - %, 10 e.g. 7.9 to 8, 2 Gew. - %, computed for elementary copper per unit of weight the concentrate, to be manufactured, which are characterised by remarkable stability when leaving untouched. Considerable for the application of the complex connections of the invention, which are diluted anyway as Algizide and/or water herbicides by the water of the operational area, is of advantage the fact that one can use the concentrates directly. Therefore concentrated solutions place of the! 5 of complex a component of the invention. If one heats usable a according to invention copper H complex up on a temperature above 100°C, for example on 100 to 130°C, preferably on 105 to 115°C and for one period of 10 min to 5 h, then one finds that 2 mole water will abgespaßen. The under splitting off from 2MolenWasser education complex connections green, hygroscopic solids represent, which separate in water and in aqueous solution under water absorption slowly a solution condition according to defined the above, according to invention used to complex connections reach. The structure according to invention used of the complex connection is to be accepted variable, however always by the definition given above characterized. It those on it that in the crystal condition only 1 mol of Alkanolamin with the hydratisierten copper IIIon is coordinated. In form of a solution, as it arises with the manufacturing process descriptive above, which is called if the complex connection in the Reak ion medium is solved, can one two molecules Alkanolamin in coordinative allocation to the hydratisierten copper H ion accept. If for example as Alkanolamin TriäLhanolamin stands, the crystalline can be regarded form cu (OI-1) 2 N (CH2 CH2 OI-1) to s, during as empirisehe formula of the reaction product in solution - without consideration of water - cu (WHETHER) 2 as empirisehe formula - without consideration of water - for [N (CH2 Ctt2 Oti) - 2 to assume is. In both cases - both in firm form and in solution - the complex is dimer. In each case that possesses copper in the complex the co-ordination number 6. The complexes specified above can become according to invention either as such inForm a concentrated solution or in dehydratisierter form on the water appliziere, preferably under attitude of ebner concentration, related to elementary copper, between 0, 1 to 10 ppm, particularly prefer 0.1 to 6 ppm, particularly 0, 2 to 1, 0 ppm in the water. The necessary concentration at complex, which corresponds to the concentrations at elementary copper, specified above, depends naturally on the percentage share of the elementary copper in the complex and lets themselves from it compute directly. The copper ii-complex connections designated above know inclusive thread algae in accordance with the invention for the fight of many forms against algae, such as Chladophora and Spirogyra, planktoniseh living algae such as Microcystis and Anabaena, branched algae such as Chara vulgaris and Mitella, in swimming basins occurring algae, which generally admit living algae as black, Braunund red algae sLnd, and in ponds and lakes such as Dietysophaerimn, Oedogoninm, Chiorococcum, Pithophora, Hydrodictyon and Lyngbya, user become. The water herbs, against those the copper ii-complexes mentioned effectively sand, particularly belong to the kinds HydrAlla vertieUiata, to Myriophyllum vertAeiiiatum, Najadaeeen etc. As the further advantage usable the according to invention complex connections exhibit a remarkably small Flschtexlzltät, like toxicity tests with Lepomis macrochirus (kind: Sormenbarsch) in the case of Kenzentrationen (weight} of 0, 5, 1, 5 and 2, 0 ppm related to elementary copper over a tent area from 8 to 96 h resulted in. Therefore the complex connections to application in waters with fish trimming are suitable. Beyond that the complex connections possess a considerably small Korrosivität and a small tendency as the further favourable characteristic for the separation of elementary copper, which in immersing tests with normal steel, stainless steel, brass, aluminum as well as Polyäthylenatreifen in aqueous solutions of the complex connections mi a content of 70 Gew. - % - related to elementary copper - was proven, whereby the Gewlchtszuwachs of the lOolyäthylenstreifen determine was examined and the appearance of the strips after one period of 29 days (17 days with stainless m steel}. Aluminum was tested additionally in 0, 8%igen solution mi Gewich sbestimmung and examination after 2, 4, 8 and 24 h. The complex connections are suitable also for application in water, which comes with machines, for example with pumps and tubes, in contact. Beyond that the complex connections, on which schen above one referred to, are remarkably stably under basischenBedingungenund are suitable itself along to the use in alkaline water, for example water with a pH between 7 and 12. The following regulations and/or examples serve the production of the active substance connections for the explanation and/or from their use according to invention. They are to limit however these in no way. Teilund percentage figures refers - so far not differently indicated - to Gew. - Parts and/or Gew. - %. The temperature specifications take place in centigrades. Regulation 1: Usable a according to invention copper H Komplexverbindung is made as follows: 680 kgTriäthanolamin (85% Triäthanolamin TEA, I5% Diäthanolamin DEA) is zugemiseht to 317, 5 1 water with about 38°. In addition one gives 226, 8 kg to copper ii-hydroxide with a copper content of 54, 5% copper and lets denKomplex to 2 h long heimaximal 58° react. After e wa 2 h adds one still to 306, 5 1 water. The copper content of the solution amounts to about 8.10%, before one filters the solution. After the Filtriefen of the solution and after cooling a copper content is determined of 7, 99%; the density of the solution with 25° amounts to 1, 202. With similar Eeaktienen small fluctuations in the content are determined. So one can receive also solutions with a content from 8, 1% copper before the Filtra ion and 8, 05% copper after the Filetierer. Furthermore will solutions with 9, 12% copper before the Filtra ion and a density from 1, 204 (25°) receive. As far as filtration is necessary, it can be e.g. managed by additive of a filter assistance of conventional kind, High flow super CelI (2% related to the solution) and filtering by means of a centrifuge and/or a sheet filter. Regulation 2:1305 1 derKupfer H HYDROXYD/TRIÄTHANOLAMIN Komplexverbindungwerden manufactured as follows: To 689.4 kg hande sü'bliehem Triä hauolamin-85 (see to example 1) gives one under agitating a) 317.5 to 1 water, b) 10, 4 kg 93%igeSehwefelsäure (to pH reconciliation) in 19 1 water and c) 200, 5 kg “copper hydrate” (“copilot by hydrates”, relatively pure copper H hydroxide without phosphate and with only traces of sulfate), which contains 62, 6% copper (molecular relationship TEA: Cu = 2: 1). After in-hour agitating the temperature of the solution amounts to 55°, and the entire “Kupferhydra “went into solution. Afterwards 325 1 water is given for solution, and agitating is continued a further quarter of an hour. After the cooling on 25° the dark-blue material ion product shows the following characteristics: A content of 8, 06% copper, specific density 1, 195, pH = 9, 8, viscosity 45 cps. After a Zei - area by weeks was not to be noticed a visible deposit oderl ällung in deu supply container, and the solution had remained clear. Regulation 3: To a solution of 298 g Triäthanolamin-99 (99% TEA, 1 o DEA) in 190 ml water gives one to 117 g basic copper sulfate [3 cu (CO2 " CuSO4, 54, 3% copper]. One agitates the mixture 2 1/2 h at winter temperature of maximally 35o. Afterwards entire basic copper sulfate went into solution. One gives still ml water to 190 to it and agitates a further quarter of an hour. With 25° the solution has a copper content of 7, 8%, a pH = 8, 7 and a specific density 1, 22 (25c). Regulation 4: To a solution, made of 301 g Triäthanolamin-99 and 190 ml, one gives 110 g to water counts. Kupferoxychlorid, [3 cu (WHETHER) 2 CuCI2, 58% cu]. One agitates the mixture 4 h long with 650. Subsequently, one admits 190 more mlWasser and agitates the mixture still another one quarter of an hour. One removes the unaufgelösten fixed portions by Flltration. As filtrate one receives a clear bluish green solution with a copper content from 8, 01%, pH = 8.4 and the specific density 1.204 (25o). Regulation 5: To a solution of 301 g Triäthanolamin-99 and 186 ml one gives basic copper carbonate [cu (OI-1) to water under agitating 120 g 2nd CuCO3, 53% cu]. The mixture is agitated 5 h with 70°. Afterwards to it one adds ml water to 180 and continues an agitating still another one quarter of an hour. After filtering the insoluble portions one receives a clear, dark-blue solution with a copper content of 7, 08%, pH = 9.4 and the specific density 1, 17 (25o). Regulation 6: A sample of the concentrated solution of the copper ii-complex connection, which one receives after the S0 procedure in accordance with regulation 1, is shifted with a surplus to acetone. The out-sewn solid body is filtered off. A part of the dried solid body (10 g) heated up without solvents with 100° i h long, whereby one becomes green the drained complex connection in form, hygroscopic solid body receives. B e i s p i e i 1: A solution of the copper hydroxide Triä hanolamin Komplexverbindung (manufactured in accordance with regulation 1) with a copper content of 8% on the water of a pond, which with thread algae and Charae (Armleuchteralge) is occupied, in a quantity one appliziert, which corresponds to a final concentration of 9,4 TpM copper in the water of the pond. In less than one week a 100%ige killing the thread algae and Charae was observed. B e I s p i egg 2: One treats living Hydrilla plants, which are held in 4 l-containers under controlled conditions in the laboratory, with inBeispieI the 1 used solution, whereby Kupferkonzentratlonen are manufactured in each case by 0, 1, 0, 2 and 0, 4 TpM. Each treatment was accomplished in each case with 6 different plant-occupied containers. After 4 weeks were mlt the highest concentration 40% killing the Hydrilla l: lances reached (S. table). Kupferkonzentratlon (Tp 0, 1 0, 2 0, 4 weeks 2% Abt& ung the Hydrilla plants after 4 0 8 17 0