CA1171426A - Copper complexes, their preparation, their use in controlling plant pests, and agents for such control - Google Patents
Copper complexes, their preparation, their use in controlling plant pests, and agents for such controlInfo
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- CA1171426A CA1171426A CA000375391A CA375391A CA1171426A CA 1171426 A CA1171426 A CA 1171426A CA 000375391 A CA000375391 A CA 000375391A CA 375391 A CA375391 A CA 375391A CA 1171426 A CA1171426 A CA 1171426A
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
- A01N37/04—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof polybasic
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/13—Dicarboxylic acids
- C07C57/145—Maleic acid
Abstract
ABSTRACT OF THE DISCLOSURE
A pesticidal composition containing a plant-tolerated copper ammino salt of a polycarboxylic acid, wherein the acid is a coploymer of 60 to 100% of acrylic acid or methacrylic acid and 0 to 40% of an acrylic acid ester or methacrylic acid ester.
A pesticidal composition containing a plant-tolerated copper ammino salt of a polycarboxylic acid, wherein the acid is a coploymer of 60 to 100% of acrylic acid or methacrylic acid and 0 to 40% of an acrylic acid ester or methacrylic acid ester.
Description
7~
O~Z. 0050~034~30/
Copper complexes, their preparation, their use in control-ling plant pests, and agents for such control _ Copper salts have long been employed in agricul-ture for the control of fungal diseases of crop plants.
To ensure that the copper treatment of the crops remains effective for a lengthy period, sparingly water-soluble, or water-insoluble, inorganic copper salts, for example copper oxychloride, are generally employed. In recent times, oily formulations of copper salts based on low mole-cular weight organic carboxylic acids have also been dis-closed (cf. The Technical Bulletin on Complex-200 from Complex Quimica S.A.); for the same activity, these have a substantially lower copper content than that of the con-ventional products.
Further, British Patent 1,394,990 has disclosed water-soluble copolymers which are claimed to be produced by polymerizing 20 60 parts of acrylic acid or methacrylic acid, 20-70 parts of an alkyl acrylate or alkyl methacryl-late and 5-20 parts of a plasticizing monomer, and in ~ which crop protection agents are to be embedded.
; The acidic copolymers are also said to be combinable, in the form of their copper salts, with the crop protection agent. However, in our own attempts to re-peat the results of this British patent, we did not obtain any useful products.
Finally, German Laid-Open Application DOS
O~Z. 0050~034~30/
Copper complexes, their preparation, their use in control-ling plant pests, and agents for such control _ Copper salts have long been employed in agricul-ture for the control of fungal diseases of crop plants.
To ensure that the copper treatment of the crops remains effective for a lengthy period, sparingly water-soluble, or water-insoluble, inorganic copper salts, for example copper oxychloride, are generally employed. In recent times, oily formulations of copper salts based on low mole-cular weight organic carboxylic acids have also been dis-closed (cf. The Technical Bulletin on Complex-200 from Complex Quimica S.A.); for the same activity, these have a substantially lower copper content than that of the con-ventional products.
Further, British Patent 1,394,990 has disclosed water-soluble copolymers which are claimed to be produced by polymerizing 20 60 parts of acrylic acid or methacrylic acid, 20-70 parts of an alkyl acrylate or alkyl methacryl-late and 5-20 parts of a plasticizing monomer, and in ~ which crop protection agents are to be embedded.
; The acidic copolymers are also said to be combinable, in the form of their copper salts, with the crop protection agent. However, in our own attempts to re-peat the results of this British patent, we did not obtain any useful products.
Finally, German Laid-Open Application DOS
2,807,293 and U.S. Patent 3,900,504 disclose copper ammine complexes which have a fungicidal action, but are not suitable for spraying plants since they do not adhere thereto.
l'7~
We have found simple copper-containiny complexes which possess good properties, especially Eor use in crop protection.
The present invention relates to a pesticidal composition con-taining a plant-tolerated copper ammine salt of a polycarboxylic acid, wherein the acid is a copolymer of 60 to 100% of acrylic acid or methacrylic acid and 0 to 40%
of an acrylic acid ester or methacrylic acid ester.
The copper'is in par-ticular in the form o an 10- ammine complex; the ammonia in the complex can ~n part also be replaced by low molecular weight volatile amines, such as methylamine. Examples of sui-table anions are those of fatty acids of 4 to 20, preferably 5 to 12, carbon a-toms, or of polybasic carboxylic acids of up to 12 carbon atoms, preferably dicarboxylic acids of up to 6 carbon atoms.
Interesting examples of such acids ar,e ethylhexanoic acid, fatty acids, such as lauric acid or oleic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, and mixtures of monobasic and/or polybasic carboxylic acids.
Particularly,useful anions have proved to be those of - polymeric carboxylic acids, for example of polymers prepared from acrylic acid, methacrylic acid and maleic acid and from their copolymers with acrylic acid esters, methacrylic acld esters and/or vlnyl compounds, for example vinyl acetate, styrene or vinyl chloride, or from mixtures of the above with one another or with the acids mentioned in the preceding paragraph.-- Other comonomers can also be present as copolymer-ized units in the above polymeric acids, for example com-,'~' , '' .
O.Z. 0050/034430/
_ 3 _ 034504/034723 plex-forming monomers, eg. acrolein, hydroxypropyl acryl-ate, butanediol monoacrylate-acet;oacetate or vinylimid-azole, and/or neutral monomers, eg. acrylamide, methacryl-amide or N-methylol methacrylamicle, and/or other anionic monomers, eg. acrylamidomethylpropanesulfonic acid and its salts, and/or cationic monomers, eg. dimethylaminoethyl methacrylate or diethylaminoethyl acrylamide, or their quaternized cationic forms.
Mixtures of an aqueous solution of a copper ammine salt and an aqueous solution of the ammonium salt of a polymer which consists of 60 - 100% of acrylic acid or methacrylic acid and 0 - 40% of an acrylic acid ester or methacrylic acid ester, as copolymerized units, have proved particularly advantageous.
It is not necessary for ~the copper ammine salts employed as crop protection agents to be~pure. ~_ The novel crop protection agent preferably con-tains from 0.01 to 10% of copper.
The copper salts according to the invention are most simply prepared by adding ammonia or an amine to an easily soluble copper salt, such as copper(II) sulfate, after which the carboxylic acid is added. They can also be prepared by reacting a copper salt of a weak or vola-tile acid with the carboxylic acids or polycarboxylic acids, which may or may not have been partially neutral-ized with ammonia, and then reacting the products with ammonia or aqueous ammonia. The reactants are employed in about the molar ratio. A substantial excess of acid 1>J~
O.Z. 0050/034430/
is a disadvantage; an excess of ammonia or amine does not interfere, but if a less than equivalent amount is used, precipitates can form, especially on diluting the product with water to the appropriate use concentrations.
The polymers can be obtained by the conventional methods of mass polymerization, solution polymerization, precipitation polymerization, emulsion polymerization or suspension polymerization.
For example, the monomers can be dissolved, in the absence of oxygen, in a 1:1 mixture of isopropanol and water, to give a 10-50% strength solution. About 0.5-5%
(based on the amount of monomers) of a polymerization initiator, for example azo-bis-isobutyronitrile, is added and the mixture is heated for 5 hours at 80C. The poly-mers obtained are used, either direct or after isolation, to prepare the novel crop protection agent.
The Examples which follow, and in which all amounts and percentages are by weight, illustrate the invention.
~XAMPLE 1 A solution of 28 parts of ethylhexanoic acid in 25 parts of ethanol, 50 parts of water and 50 parts of con-centrated ammonia is added to a stirred solution of 20 parts of CuS04.5H20 in 50 parts of water and 30 parts of concentrated ammonia. A deep blue, clear solution re-sults, which is miscible with water in all proportions.
On drying the (dilute) solution at room temperature, a sparingly water-soluble copper compound results.
- 1 ~'7~
O,Z~ 0050/034430/
- 5 - 03~50~/034723 A solution of 50 parts of oleic acid in 25 parts of ethanol, 75 parts of water and 50 parts of concentrated ammonia is added to a stirred solution of 20 parts of CuS04.5H20 in 50 parts of water and 30 parts of concen-trated ammonia. The resulting deep blue solution is di-luted with water in the ratio of 5 parts of solution to g5 parts of water, giving a milky blue emulsion which over 24 hours shows only slight creaming.
The insoluble copper salt which results on drying is difficult to wet with water.
A solution of 20 parts of a dicarboxylic acid mix-ture of about 30% by weight of succinic acid, 40% by weight of glutaric acid and 30% by weight of adipic acid in 40 parts of water and 20 parts of concentrated ammonia is added to a stirred solution of 38 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated ammonia.
The resulting deep blue solution gives a clear mixture with water in all proportions. On drying, a water-insoluble copper residue results.
^ A solution of 30 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated ammonia is added to a stirred solution, in 96.25 parts of water and 3.75 parts of concentrated ammonia, of a solution copolymer which has been obtained from 6.7 parts of methyl acrylate and 13.3 parts of acrylic acid and has a K value of 46.
The resulting deep blue clear solution is stable on stor-, ~ :~'7 ~ ~2~i O~Z. 0050/034430/
- 6 - 034504/03~723 age and miscible with water in all proportions. The copper content of the solution is 2.87%.
The procedure described in Example 4 is followed, except that a solution copolymer obtained from 6.7 parts of ethyl acrylate and 13.3 parts of acrylic acid and hav-ng a K value of 42 is used.
The ~rocedure described in Example 4 is followed, except that a solution ~polymer obtained from 6.7 parts of n-butyl acrylate and 13.3 parts of acrylic acid and hav~
ing a K value of 41 is used.
37.5 parts of water and 7.5 parts of concentrated ammonia are added to a 50% strength solution, in a 1:1 isopropanol/water mixture, of a copolymer obtained from 25.1 parts of acrylic acid and 12.4 parts of n-butyl ' acrylate and having a K value of 48. 60 parts of CuS04.5H20 are then dissolved in 50 parts of hot water and when this solution has cooled, 120 parts of concen-trated ammonia are added. The solutions abtained are combined. A deep blue, clear solution results, which is stable on storage and is miscible,with water in all proportions. The copper content of the solution is 4.36%.
37.5 parts of water and 3.75 parts of concentrated ammonia are added to a 25% strength solution, in a 1:1 isopropanol/water mixture, of a copolymer obtained from :
~:~'J'~
O.Z. 0050/03~30/
_ 7 _ 03~50~/034723 12.5 parts of acrylic acid and 6.2 parts of n-butyl acry-late and having a K value of 43. 20 parts of CuS04.5H20 are dissolved in 75 parts of hot water. The solution is cooled and 35 parts of concentrated ammonia are added. The solutions ob-tained are combined. The copper content of the solution is 2.11%.
A solution of 30 parts of CuS04.5H20 in 60 parts of concentrated ammonia is added to a solution, in 33 parts of water and 10 parts of concentrated ammonial of a solution polymer obtained from 4.5 parts of acrylic acid and having a K value of 20. The resulting deep blue solution is stable on storage and is miscible with water in all proportions. The copper content of the solu-tion is 5.53%
A solution, in 49 parts of water and 10 parts of concentrated ammonia, of a solution polymer obtained from 4.5 parts of acrylic acid and having a K value of about 20 is added dropwise to a solution of 45 parts of CuS04.5H20 in 90 parts of concentrated ammonia. The copper content of the solution is 5.78%.
A mixture of 10 parts of a 25% strength solution of polymethacrylic acid, having a K value of 60, in pro-pylene glycol, and 10 parts of water is slowly added dropwise to a stirred solution of 15 parts of CuS04.H20 in 10 parts of water and 40 parts of concentrated aqueous ammonia. A deep blue clear solution is obtained, which O,Z. 0050/034g30/
- 8 - 034504/03~723 is miscible with water in all prop~rtions. On drying the (dilute) solution at room temperature, a sparingly water-soluble copper compound results.
A mixture of 3~ parts of a 40% strength disper-sion of an emulsion copolymer of 90% by weight of n-butyl acrylate and 10% by weight of acrylic acid, ~0 parts of water and 3 parts of concentrated aqueous ammonia is slowly added dropwise to a solution of 11 parts of CuS04.5H20 in 15 parts of water and 25 parts of concen-trated aqueous ammonia. A blue milky cloudy dispersion is obtained, which is miscible with water in all propor-tions and on drying at room temperature gives a water--- resistant film.
EXA~PLE 13 A mixture of 10 parts of a 50% strength solution of a polyacrylic acid, ha~ring a K value of 25, 10 parts -~ of concentrated aqueous ammonia and 43 parts of water is slowly added dropwise to a solution of 45 parts of CuS04.5H20 in 90 parts of concentrated aqueous ammonia.
The resulting deep blue clear solution is mixed in a ratio of 1:1 with Acronal 567 D plastics dispersion~
The resulting blue mil~y cloudy dispersion is miscible with water in all proportions and, on drying, gives a water-resistant film.
A solution of 75 parts of a 50% strength solu-tion of a copolymer of 33% by weight 0,Z. OOS0/034430/
_ g _ 034504/034723 of n-butyl acrylate, 65% by weight of acrylic acid and 2%
by weight of dimethylaminoethyl rnethacrylate, which has been quaternized with methyl chloride and has a K value of 48, 37.5 parts of water and 7.5 parts of concentrated aqueous ammonia is added to a st:irred solution of 60 parts of CuS04.5H20 in 50 parts of water and 120 parts of concentrated aqueous ammonia. A deep blue solution is obtained, which is stable on storage, is miscible with water in all proportions, and on drying gives a water-resistant residue.
A mixture of 75 parts of a 25% strength solution~a co~Qlymer of~ 33% by~ _ _.
weight of tert.-butyl acrylate and 67o/o ~-wsight ---of acrylic acid, havlng a K value of 45, 37.5 parts by weight of water and 3.75 parts by weight of concentrated aqueous ammonia is added to a stirred solution of 30 parts of CuS0~.5~20 in 75 parts of water and 45 parts of concentrated aqueous ammonia. The resulting deep blue solution is stable on storage, is miscible with water in all proportions, and on drying gives a brittle, water-resistant residue.
A clear solution of 75 parts of a 25% strength solution a~ a :copol~mer of 33~ by `~
weight of n-butyl acrylate and 67% by weight of acrylic acid, having a K value of 40, 10 parts of oleic acid, 37.5 parts of water and 25 parts of concentrated aqueous ammonia is added to a stirred solution of 40 parts of 7~
O.Z. 0050/034430/
- lO - 03450~/03~723 CuS04.5H20 in 75 parts of water and 50 parts of concen-trated aqueous ammonia. The resulting clear deep blue solution, when diluted with water, gives an adequately stable cloudy spray liquor, which on drying leaves a copper-containing residue which swells in wa,ter, but does not dissolve.
EXAMPLE l7 A solution of 75 parts of a 25% strength ~=
so-Iution of a copolymer of 33% by weight of styrene and 67% by weight of acrylic acid, having a K value of lo 36, 3? . 5 parts of water and 3. 75 parts of concentrated aqueous ammonia is added to a stirred solution of 30 parts of CuS04.5H20 in 7S parts of water and 45 parts of aqueous ammonia. The deep blue solution is stable on storage and is miscible with water in all proportions;
on drying, a water-resistant residue is left.
150 parts ofa 25% strength aqueous solution of a copolymer of 48% by weight of vinyl imidazole and 52% by weight of acrylic acid, having a K value of 32, is added, with stirring, to 225 parts of a solution of 150 parts of CuS04.5H20 in 200 parts of water and 200 parts of concen-centrated aqueous ammonia. The resulting dark blue solution is stable on storage and is miscible with water in all proportions.
EXAMP~E l9 A solution of 50 parts of a 25% strength ~-solùtion ~ a: copolymer of 66% by weight of acrylic acid and 34% by weight of acrolein, having a K value of O.Z. 0050/034~30 32, and 6 parts of concentrated aqueous ammonia is added, with stirring, to 175 parts of a solution of 150 parts of CuS04.5H20 in 400 parts of half-concentrated aqueous ammo-nia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, lea~es a water-resistant fungicidal residue.
A mixture of 100 parts of a 25% strength so~ut-ion--o~- a copolymer obtained from equal amounts of.
acrylic acid, maleic anhydride and acrylamidodimethylpro-panesulfonic acid and having a K value of 31, 60 parts ofwater and 20 parts of concentrated aqueous ammonia is added, with stirring, to 180 parts by weight-of a solution of 150 parts of CuS04.5H20 in 400 parts of half-concentrated aqueous ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, leaves a water-resistant residue.
A mixture of 50 parts of a 25% strength - _ ~o~ ~ on~ of~ ~ : copolymer of 50% by weight of acrylic acid, 16% by weight of acrolein, 17% by weight of n-butyl acrylate and 17% by weight of methyl methacrylate, having a K value of 15.5, 100 parts of water and 50 parts of concentrated aqueous ammonia is added to 110 parts of a 27% strength solution of CuS04.5H20 in half-concentrated aqueous ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, lea-ves a water-resistant copper-containing residue.
~ ~'7 ~ 6 2 O~Z. 0050/034~30/
~ ~ 03~504/~3~723 A mixture of 100 parts of a 25% strength solution o~ a copolymer of 90% by weight of acrylic acid and 10% by weight of N-methylol methacrylamide, hav-ing a K value of 481 100 parts of water and 20 parts of concentrated aqueous ammonia is added to 290 parts of a 27% strength solution of CuS04.5H20 in half-concentrated ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on dry-ing, leaves a water-resistant residue.
10A mixture of 75 parts of a 25% strength solution;~o~f a copolymer of 80% by weight of acrylic acid and 20% by weight of a reaction product of equimolar amounts of hydroxypropyl acrylate and ketene, 37.5 parts by weight of water and 3.75 parts by weight of concen-trated aqueous ammonia is added dropwise to a stirred - solution of 30 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated aqueous ammonia. The re-sulting solution is stabIe on storage and miscible with water in all proportions, and, on drying, leaves a water-resistant residue.
The procedure described in Example 23 is followed, except that in place of the copolymer of acrylic acid and hydroxypropyl acrylate-acetoacetate, a terpolymer of 40%
by weight of acrylic acid, 40% by weight of methacrylic acid and 20% by weight of a reaction product of equimolar amounts of hydroxypropyl acrylate and ketene is employed.
O.Z. 0050/03~430/
If the novel crop protection agent, diluted to the use concentration, is applied to articles, plants or plant parts which are to be treated, the solution, as it dries, leaves a metal poly-salt which is sparingly water-soluble, or water-insoluble, s~i~ck-s_ firmly to the article or plant, and retains its fungicidal and/or bac-tericidal action for a long period.
The novel complexes have, for example, an excel-lent fungicidal action which surpasses that of the con-ventional copper-containing ~ungicides. They can therefore be employed wherever undesired growth of, or infestation by, organisms is encountered. Examples include the inhibition o~ infestation, by bacteria, algae, fungi, lichen and moss, of plants, building materials, such as natural and artifical stone, flagglng, rendering, plaster and paint, and wooden articles exposed to water.
In particular, the novel complexes may be used to control Phytophthora infestans in tomatoes and potatoes, Plasmo-para viticola in vines, Pseudoperonospora humuli in hops, Cercospora beticolain. bee~jCercospora musae-in bananas, Venturia inaequalis in apples, Exobasidium vexans in tea and Hemileia vastatrix in coffee.
Surprisingly, the novel crop protection agents are also excellent bactericides for controlling plant bacterioses. The following are examples of bacterioses which can be controlled with the novel agents: Coryne-bacterium michiganense in tobacco, Erwinia amylovora i~
pears and apples, Erwinia carotovora in.potatoes, Pseudo-monas lachrymans in cucumbers, Pseudomonas phaseolicola :1 ~'7~
O~Z. 0050/034430/
in beans, Pseudomonas syringae in lilac, Pseudomonas solanacearum in bananas, Xanthomonas campestris in cabba~e~
Xanthomonas malvacearum in cotton and Xanthomonas oryzae in rice.
In contrast to the best of the highly acti~e copper compounds, the novel act:Lve ingredïents, and the agents prepared therewith, are very well tolerated by plants, even in the case of sensitive crops such as pears and apples~.
The novel crop protection agents have the further advantage that they can be applied from purely aqueous solution. Hence, their use causes less pollution of the environment than does the treatment with conventional copper compounds.
As a rule, the novel crop protection agents form, after spraying, a coating which sticks firmly to the treated articles or plants. However, if adhesion difficulties arise, a sticker may be added. An example of a suitable sticker is a styrene/n-butyl acrylate dispersion obtainable under the trademark ~ Acronal 567 Do The use formulations of the novel agents can additionallycontain otherac-tive ingredien-ts, such asherbi-cides, insecticides, growth regulators or fungicidesO
The Examples which follow illustrate the biologi-cal action.
- 15 - -Z~ 0050/03~430/
03~504/034723 EXAMPLE A
Fungicidal activity of the active in~redients of Examples 4 -10 on Phytophthora infestans in tomataes.
Leaves of tomato plants of the Professor Rudloff variety are sprayed with aqueous solutions which contain 0.024, 0~012, 0.006 and 0.003% of copper (calculated as metal). When the spray coating has dried, the leaves - are infected with a zoospore suspension of the fungus ` Phytophthora infestans. The plants are then placed in a water vapor-saturated chamber at from 16 to 18C.
After 5 days, the disease has developed sufficiently on the untreated infected control plants for the fungicidal activity of the compounds to be assessed.
The experiment shows that solutlons containing about 0.01% of copper very effectively inhibit infec-tion. The fungicides of Examples 3, 6, 7 and 8 prove particularly advantagsous.
EXAMPLE B
Bactericidal action on Erwinia amylovora in pears.
a) Pear trees of the Conference variety, in an area in which the fire blight caused by the bacterium Erwinia 20~ amylovora is particularly prevalent,were treated at week-ly intervals, a total of ten times, with an 0.25%
strength solution of the active ingredient from Example 4. Of 40 treated trees, only one showed an area of infection; on the same number of untreated trees, 37 areas of infection were found.
b) Pear trees weresprayed, in the same manner as des-cribed under a), with an 0.25% strength solution of the O.Z. 0050/03~430/
- 16 - 034504/03~723 active ingredient from Example 5. Areas of in~ection were found on only 3 out of 40 trees.
There was no visible damage to the trees after treatment.
EXAMPLE C
Plant toleration.
Apple seedlings of the Golden Delicious variety, in the 9-leaf-stage,were sprayed to run-off with an aqueous solution containing 0.04% of copper (calculated as metal). The test plants wereplaced in a climatic-ally controlled chamber at 18C, under additional illumi-nation. 14 days after spraying, the extent o~ the damage to the plants was assessed.
In this experiment, the Complex 200 formulation produced leaf damage (necroses) at concentrations at which, for example, the compound of Example 5 was satis-factorily tolerated.
~ ~ ' ' ' .
'
l'7~
We have found simple copper-containiny complexes which possess good properties, especially Eor use in crop protection.
The present invention relates to a pesticidal composition con-taining a plant-tolerated copper ammine salt of a polycarboxylic acid, wherein the acid is a copolymer of 60 to 100% of acrylic acid or methacrylic acid and 0 to 40%
of an acrylic acid ester or methacrylic acid ester.
The copper'is in par-ticular in the form o an 10- ammine complex; the ammonia in the complex can ~n part also be replaced by low molecular weight volatile amines, such as methylamine. Examples of sui-table anions are those of fatty acids of 4 to 20, preferably 5 to 12, carbon a-toms, or of polybasic carboxylic acids of up to 12 carbon atoms, preferably dicarboxylic acids of up to 6 carbon atoms.
Interesting examples of such acids ar,e ethylhexanoic acid, fatty acids, such as lauric acid or oleic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, and mixtures of monobasic and/or polybasic carboxylic acids.
Particularly,useful anions have proved to be those of - polymeric carboxylic acids, for example of polymers prepared from acrylic acid, methacrylic acid and maleic acid and from their copolymers with acrylic acid esters, methacrylic acld esters and/or vlnyl compounds, for example vinyl acetate, styrene or vinyl chloride, or from mixtures of the above with one another or with the acids mentioned in the preceding paragraph.-- Other comonomers can also be present as copolymer-ized units in the above polymeric acids, for example com-,'~' , '' .
O.Z. 0050/034430/
_ 3 _ 034504/034723 plex-forming monomers, eg. acrolein, hydroxypropyl acryl-ate, butanediol monoacrylate-acet;oacetate or vinylimid-azole, and/or neutral monomers, eg. acrylamide, methacryl-amide or N-methylol methacrylamicle, and/or other anionic monomers, eg. acrylamidomethylpropanesulfonic acid and its salts, and/or cationic monomers, eg. dimethylaminoethyl methacrylate or diethylaminoethyl acrylamide, or their quaternized cationic forms.
Mixtures of an aqueous solution of a copper ammine salt and an aqueous solution of the ammonium salt of a polymer which consists of 60 - 100% of acrylic acid or methacrylic acid and 0 - 40% of an acrylic acid ester or methacrylic acid ester, as copolymerized units, have proved particularly advantageous.
It is not necessary for ~the copper ammine salts employed as crop protection agents to be~pure. ~_ The novel crop protection agent preferably con-tains from 0.01 to 10% of copper.
The copper salts according to the invention are most simply prepared by adding ammonia or an amine to an easily soluble copper salt, such as copper(II) sulfate, after which the carboxylic acid is added. They can also be prepared by reacting a copper salt of a weak or vola-tile acid with the carboxylic acids or polycarboxylic acids, which may or may not have been partially neutral-ized with ammonia, and then reacting the products with ammonia or aqueous ammonia. The reactants are employed in about the molar ratio. A substantial excess of acid 1>J~
O.Z. 0050/034430/
is a disadvantage; an excess of ammonia or amine does not interfere, but if a less than equivalent amount is used, precipitates can form, especially on diluting the product with water to the appropriate use concentrations.
The polymers can be obtained by the conventional methods of mass polymerization, solution polymerization, precipitation polymerization, emulsion polymerization or suspension polymerization.
For example, the monomers can be dissolved, in the absence of oxygen, in a 1:1 mixture of isopropanol and water, to give a 10-50% strength solution. About 0.5-5%
(based on the amount of monomers) of a polymerization initiator, for example azo-bis-isobutyronitrile, is added and the mixture is heated for 5 hours at 80C. The poly-mers obtained are used, either direct or after isolation, to prepare the novel crop protection agent.
The Examples which follow, and in which all amounts and percentages are by weight, illustrate the invention.
~XAMPLE 1 A solution of 28 parts of ethylhexanoic acid in 25 parts of ethanol, 50 parts of water and 50 parts of con-centrated ammonia is added to a stirred solution of 20 parts of CuS04.5H20 in 50 parts of water and 30 parts of concentrated ammonia. A deep blue, clear solution re-sults, which is miscible with water in all proportions.
On drying the (dilute) solution at room temperature, a sparingly water-soluble copper compound results.
- 1 ~'7~
O,Z~ 0050/034430/
- 5 - 03~50~/034723 A solution of 50 parts of oleic acid in 25 parts of ethanol, 75 parts of water and 50 parts of concentrated ammonia is added to a stirred solution of 20 parts of CuS04.5H20 in 50 parts of water and 30 parts of concen-trated ammonia. The resulting deep blue solution is di-luted with water in the ratio of 5 parts of solution to g5 parts of water, giving a milky blue emulsion which over 24 hours shows only slight creaming.
The insoluble copper salt which results on drying is difficult to wet with water.
A solution of 20 parts of a dicarboxylic acid mix-ture of about 30% by weight of succinic acid, 40% by weight of glutaric acid and 30% by weight of adipic acid in 40 parts of water and 20 parts of concentrated ammonia is added to a stirred solution of 38 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated ammonia.
The resulting deep blue solution gives a clear mixture with water in all proportions. On drying, a water-insoluble copper residue results.
^ A solution of 30 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated ammonia is added to a stirred solution, in 96.25 parts of water and 3.75 parts of concentrated ammonia, of a solution copolymer which has been obtained from 6.7 parts of methyl acrylate and 13.3 parts of acrylic acid and has a K value of 46.
The resulting deep blue clear solution is stable on stor-, ~ :~'7 ~ ~2~i O~Z. 0050/034430/
- 6 - 034504/03~723 age and miscible with water in all proportions. The copper content of the solution is 2.87%.
The procedure described in Example 4 is followed, except that a solution copolymer obtained from 6.7 parts of ethyl acrylate and 13.3 parts of acrylic acid and hav-ng a K value of 42 is used.
The ~rocedure described in Example 4 is followed, except that a solution ~polymer obtained from 6.7 parts of n-butyl acrylate and 13.3 parts of acrylic acid and hav~
ing a K value of 41 is used.
37.5 parts of water and 7.5 parts of concentrated ammonia are added to a 50% strength solution, in a 1:1 isopropanol/water mixture, of a copolymer obtained from 25.1 parts of acrylic acid and 12.4 parts of n-butyl ' acrylate and having a K value of 48. 60 parts of CuS04.5H20 are then dissolved in 50 parts of hot water and when this solution has cooled, 120 parts of concen-trated ammonia are added. The solutions abtained are combined. A deep blue, clear solution results, which is stable on storage and is miscible,with water in all proportions. The copper content of the solution is 4.36%.
37.5 parts of water and 3.75 parts of concentrated ammonia are added to a 25% strength solution, in a 1:1 isopropanol/water mixture, of a copolymer obtained from :
~:~'J'~
O.Z. 0050/03~30/
_ 7 _ 03~50~/034723 12.5 parts of acrylic acid and 6.2 parts of n-butyl acry-late and having a K value of 43. 20 parts of CuS04.5H20 are dissolved in 75 parts of hot water. The solution is cooled and 35 parts of concentrated ammonia are added. The solutions ob-tained are combined. The copper content of the solution is 2.11%.
A solution of 30 parts of CuS04.5H20 in 60 parts of concentrated ammonia is added to a solution, in 33 parts of water and 10 parts of concentrated ammonial of a solution polymer obtained from 4.5 parts of acrylic acid and having a K value of 20. The resulting deep blue solution is stable on storage and is miscible with water in all proportions. The copper content of the solu-tion is 5.53%
A solution, in 49 parts of water and 10 parts of concentrated ammonia, of a solution polymer obtained from 4.5 parts of acrylic acid and having a K value of about 20 is added dropwise to a solution of 45 parts of CuS04.5H20 in 90 parts of concentrated ammonia. The copper content of the solution is 5.78%.
A mixture of 10 parts of a 25% strength solution of polymethacrylic acid, having a K value of 60, in pro-pylene glycol, and 10 parts of water is slowly added dropwise to a stirred solution of 15 parts of CuS04.H20 in 10 parts of water and 40 parts of concentrated aqueous ammonia. A deep blue clear solution is obtained, which O,Z. 0050/034g30/
- 8 - 034504/03~723 is miscible with water in all prop~rtions. On drying the (dilute) solution at room temperature, a sparingly water-soluble copper compound results.
A mixture of 3~ parts of a 40% strength disper-sion of an emulsion copolymer of 90% by weight of n-butyl acrylate and 10% by weight of acrylic acid, ~0 parts of water and 3 parts of concentrated aqueous ammonia is slowly added dropwise to a solution of 11 parts of CuS04.5H20 in 15 parts of water and 25 parts of concen-trated aqueous ammonia. A blue milky cloudy dispersion is obtained, which is miscible with water in all propor-tions and on drying at room temperature gives a water--- resistant film.
EXA~PLE 13 A mixture of 10 parts of a 50% strength solution of a polyacrylic acid, ha~ring a K value of 25, 10 parts -~ of concentrated aqueous ammonia and 43 parts of water is slowly added dropwise to a solution of 45 parts of CuS04.5H20 in 90 parts of concentrated aqueous ammonia.
The resulting deep blue clear solution is mixed in a ratio of 1:1 with Acronal 567 D plastics dispersion~
The resulting blue mil~y cloudy dispersion is miscible with water in all proportions and, on drying, gives a water-resistant film.
A solution of 75 parts of a 50% strength solu-tion of a copolymer of 33% by weight 0,Z. OOS0/034430/
_ g _ 034504/034723 of n-butyl acrylate, 65% by weight of acrylic acid and 2%
by weight of dimethylaminoethyl rnethacrylate, which has been quaternized with methyl chloride and has a K value of 48, 37.5 parts of water and 7.5 parts of concentrated aqueous ammonia is added to a st:irred solution of 60 parts of CuS04.5H20 in 50 parts of water and 120 parts of concentrated aqueous ammonia. A deep blue solution is obtained, which is stable on storage, is miscible with water in all proportions, and on drying gives a water-resistant residue.
A mixture of 75 parts of a 25% strength solution~a co~Qlymer of~ 33% by~ _ _.
weight of tert.-butyl acrylate and 67o/o ~-wsight ---of acrylic acid, havlng a K value of 45, 37.5 parts by weight of water and 3.75 parts by weight of concentrated aqueous ammonia is added to a stirred solution of 30 parts of CuS0~.5~20 in 75 parts of water and 45 parts of concentrated aqueous ammonia. The resulting deep blue solution is stable on storage, is miscible with water in all proportions, and on drying gives a brittle, water-resistant residue.
A clear solution of 75 parts of a 25% strength solution a~ a :copol~mer of 33~ by `~
weight of n-butyl acrylate and 67% by weight of acrylic acid, having a K value of 40, 10 parts of oleic acid, 37.5 parts of water and 25 parts of concentrated aqueous ammonia is added to a stirred solution of 40 parts of 7~
O.Z. 0050/034430/
- lO - 03450~/03~723 CuS04.5H20 in 75 parts of water and 50 parts of concen-trated aqueous ammonia. The resulting clear deep blue solution, when diluted with water, gives an adequately stable cloudy spray liquor, which on drying leaves a copper-containing residue which swells in wa,ter, but does not dissolve.
EXAMPLE l7 A solution of 75 parts of a 25% strength ~=
so-Iution of a copolymer of 33% by weight of styrene and 67% by weight of acrylic acid, having a K value of lo 36, 3? . 5 parts of water and 3. 75 parts of concentrated aqueous ammonia is added to a stirred solution of 30 parts of CuS04.5H20 in 7S parts of water and 45 parts of aqueous ammonia. The deep blue solution is stable on storage and is miscible with water in all proportions;
on drying, a water-resistant residue is left.
150 parts ofa 25% strength aqueous solution of a copolymer of 48% by weight of vinyl imidazole and 52% by weight of acrylic acid, having a K value of 32, is added, with stirring, to 225 parts of a solution of 150 parts of CuS04.5H20 in 200 parts of water and 200 parts of concen-centrated aqueous ammonia. The resulting dark blue solution is stable on storage and is miscible with water in all proportions.
EXAMP~E l9 A solution of 50 parts of a 25% strength ~-solùtion ~ a: copolymer of 66% by weight of acrylic acid and 34% by weight of acrolein, having a K value of O.Z. 0050/034~30 32, and 6 parts of concentrated aqueous ammonia is added, with stirring, to 175 parts of a solution of 150 parts of CuS04.5H20 in 400 parts of half-concentrated aqueous ammo-nia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, lea~es a water-resistant fungicidal residue.
A mixture of 100 parts of a 25% strength so~ut-ion--o~- a copolymer obtained from equal amounts of.
acrylic acid, maleic anhydride and acrylamidodimethylpro-panesulfonic acid and having a K value of 31, 60 parts ofwater and 20 parts of concentrated aqueous ammonia is added, with stirring, to 180 parts by weight-of a solution of 150 parts of CuS04.5H20 in 400 parts of half-concentrated aqueous ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, leaves a water-resistant residue.
A mixture of 50 parts of a 25% strength - _ ~o~ ~ on~ of~ ~ : copolymer of 50% by weight of acrylic acid, 16% by weight of acrolein, 17% by weight of n-butyl acrylate and 17% by weight of methyl methacrylate, having a K value of 15.5, 100 parts of water and 50 parts of concentrated aqueous ammonia is added to 110 parts of a 27% strength solution of CuS04.5H20 in half-concentrated aqueous ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on drying, lea-ves a water-resistant copper-containing residue.
~ ~'7 ~ 6 2 O~Z. 0050/034~30/
~ ~ 03~504/~3~723 A mixture of 100 parts of a 25% strength solution o~ a copolymer of 90% by weight of acrylic acid and 10% by weight of N-methylol methacrylamide, hav-ing a K value of 481 100 parts of water and 20 parts of concentrated aqueous ammonia is added to 290 parts of a 27% strength solution of CuS04.5H20 in half-concentrated ammonia. The resulting solution is stable on storage and miscible with water in all proportions, and, on dry-ing, leaves a water-resistant residue.
10A mixture of 75 parts of a 25% strength solution;~o~f a copolymer of 80% by weight of acrylic acid and 20% by weight of a reaction product of equimolar amounts of hydroxypropyl acrylate and ketene, 37.5 parts by weight of water and 3.75 parts by weight of concen-trated aqueous ammonia is added dropwise to a stirred - solution of 30 parts of CuS04.5H20 in 75 parts of water and 45 parts of concentrated aqueous ammonia. The re-sulting solution is stabIe on storage and miscible with water in all proportions, and, on drying, leaves a water-resistant residue.
The procedure described in Example 23 is followed, except that in place of the copolymer of acrylic acid and hydroxypropyl acrylate-acetoacetate, a terpolymer of 40%
by weight of acrylic acid, 40% by weight of methacrylic acid and 20% by weight of a reaction product of equimolar amounts of hydroxypropyl acrylate and ketene is employed.
O.Z. 0050/03~430/
If the novel crop protection agent, diluted to the use concentration, is applied to articles, plants or plant parts which are to be treated, the solution, as it dries, leaves a metal poly-salt which is sparingly water-soluble, or water-insoluble, s~i~ck-s_ firmly to the article or plant, and retains its fungicidal and/or bac-tericidal action for a long period.
The novel complexes have, for example, an excel-lent fungicidal action which surpasses that of the con-ventional copper-containing ~ungicides. They can therefore be employed wherever undesired growth of, or infestation by, organisms is encountered. Examples include the inhibition o~ infestation, by bacteria, algae, fungi, lichen and moss, of plants, building materials, such as natural and artifical stone, flagglng, rendering, plaster and paint, and wooden articles exposed to water.
In particular, the novel complexes may be used to control Phytophthora infestans in tomatoes and potatoes, Plasmo-para viticola in vines, Pseudoperonospora humuli in hops, Cercospora beticolain. bee~jCercospora musae-in bananas, Venturia inaequalis in apples, Exobasidium vexans in tea and Hemileia vastatrix in coffee.
Surprisingly, the novel crop protection agents are also excellent bactericides for controlling plant bacterioses. The following are examples of bacterioses which can be controlled with the novel agents: Coryne-bacterium michiganense in tobacco, Erwinia amylovora i~
pears and apples, Erwinia carotovora in.potatoes, Pseudo-monas lachrymans in cucumbers, Pseudomonas phaseolicola :1 ~'7~
O~Z. 0050/034430/
in beans, Pseudomonas syringae in lilac, Pseudomonas solanacearum in bananas, Xanthomonas campestris in cabba~e~
Xanthomonas malvacearum in cotton and Xanthomonas oryzae in rice.
In contrast to the best of the highly acti~e copper compounds, the novel act:Lve ingredïents, and the agents prepared therewith, are very well tolerated by plants, even in the case of sensitive crops such as pears and apples~.
The novel crop protection agents have the further advantage that they can be applied from purely aqueous solution. Hence, their use causes less pollution of the environment than does the treatment with conventional copper compounds.
As a rule, the novel crop protection agents form, after spraying, a coating which sticks firmly to the treated articles or plants. However, if adhesion difficulties arise, a sticker may be added. An example of a suitable sticker is a styrene/n-butyl acrylate dispersion obtainable under the trademark ~ Acronal 567 Do The use formulations of the novel agents can additionallycontain otherac-tive ingredien-ts, such asherbi-cides, insecticides, growth regulators or fungicidesO
The Examples which follow illustrate the biologi-cal action.
- 15 - -Z~ 0050/03~430/
03~504/034723 EXAMPLE A
Fungicidal activity of the active in~redients of Examples 4 -10 on Phytophthora infestans in tomataes.
Leaves of tomato plants of the Professor Rudloff variety are sprayed with aqueous solutions which contain 0.024, 0~012, 0.006 and 0.003% of copper (calculated as metal). When the spray coating has dried, the leaves - are infected with a zoospore suspension of the fungus ` Phytophthora infestans. The plants are then placed in a water vapor-saturated chamber at from 16 to 18C.
After 5 days, the disease has developed sufficiently on the untreated infected control plants for the fungicidal activity of the compounds to be assessed.
The experiment shows that solutlons containing about 0.01% of copper very effectively inhibit infec-tion. The fungicides of Examples 3, 6, 7 and 8 prove particularly advantagsous.
EXAMPLE B
Bactericidal action on Erwinia amylovora in pears.
a) Pear trees of the Conference variety, in an area in which the fire blight caused by the bacterium Erwinia 20~ amylovora is particularly prevalent,were treated at week-ly intervals, a total of ten times, with an 0.25%
strength solution of the active ingredient from Example 4. Of 40 treated trees, only one showed an area of infection; on the same number of untreated trees, 37 areas of infection were found.
b) Pear trees weresprayed, in the same manner as des-cribed under a), with an 0.25% strength solution of the O.Z. 0050/03~430/
- 16 - 034504/03~723 active ingredient from Example 5. Areas of in~ection were found on only 3 out of 40 trees.
There was no visible damage to the trees after treatment.
EXAMPLE C
Plant toleration.
Apple seedlings of the Golden Delicious variety, in the 9-leaf-stage,were sprayed to run-off with an aqueous solution containing 0.04% of copper (calculated as metal). The test plants wereplaced in a climatic-ally controlled chamber at 18C, under additional illumi-nation. 14 days after spraying, the extent o~ the damage to the plants was assessed.
In this experiment, the Complex 200 formulation produced leaf damage (necroses) at concentrations at which, for example, the compound of Example 5 was satis-factorily tolerated.
~ ~ ' ' ' .
'
Claims (3)
1. A pesticidal composition containing a plant-tolerated copper ammine salt of a polycarboxylic acid, wherein the acid is a copolymer of 60 to 100% of acrylic acid or methacrylic acid and 0 to 40% of an acrylic acid ester or methacrylic acid ester.
2. A plant fungicidal composition containing a plant-tolerated copper amine salt as defined in claim 1.
3. A plant bactericidal composition containing a plant-tolerated copper ammine salt as defined in claim 1.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803017123 DE3017123A1 (en) | 1980-05-03 | 1980-05-03 | Copper fungicide aq. solns. - of copper ammine salt and ammonium salt of (meth)acrylic! acid (co)polymer |
| DEP3017123.4 | 1980-05-03 | ||
| DEP3022432.9 | 1980-06-14 | ||
| DE19803022432 DE3022432A1 (en) | 1980-06-14 | 1980-06-14 | Copper ammine salts of organic, opt. polymeric, carboxylic acids - esp. useful as fungicides and bactericides for plant protection |
| DEP3039409.3 | 1980-10-18 | ||
| DE19803039409 DE3039409A1 (en) | 1980-10-18 | 1980-10-18 | Copper ammine salts of organic, opt. polymeric, carboxylic acids - esp. useful as fungicides and bactericides for plant protection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1171426A true CA1171426A (en) | 1984-07-24 |
Family
ID=27188610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000375391A Expired CA1171426A (en) | 1980-05-03 | 1981-04-14 | Copper complexes, their preparation, their use in controlling plant pests, and agents for such control |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US4409358A (en) |
| EP (1) | EP0039788B1 (en) |
| AU (1) | AU538632B2 (en) |
| BR (1) | BR8102689A (en) |
| CA (1) | CA1171426A (en) |
| DE (1) | DE3161008D1 (en) |
| DK (1) | DK160910C (en) |
| ES (1) | ES8300003A1 (en) |
| GB (1) | GB2077740B (en) |
| GR (1) | GR75196B (en) |
| IE (1) | IE51149B1 (en) |
| IL (1) | IL62645A (en) |
| KE (1) | KE3432A (en) |
| MA (1) | MA19132A1 (en) |
| MY (1) | MY8600469A (en) |
| PT (1) | PT72950B (en) |
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| FI70682C (en) * | 1984-06-20 | 1987-08-05 | Kemira Oy | Wood preservative and its use as a surface treatment agent |
| US4851557A (en) * | 1985-06-20 | 1989-07-25 | Benckiser-Knapsack Gmbh | Copper-containing polymers, a process for their preparation and their use as fungicides |
| EP0208858B1 (en) * | 1985-06-20 | 1989-02-08 | Benckiser-Knapsack GmbH | Copper-containing polymers, process for their preparation, and their application as fungicides |
| US5242685A (en) * | 1986-03-15 | 1993-09-07 | Basf Aktiengesellschaft | Copper-containing agent for controlling fungi and bacteria |
| DE3608681A1 (en) * | 1986-03-15 | 1987-09-17 | Basf Ag | COPPER CONTAINER FOR CONTROLLING MUSHROOMS AND BACTERIA |
| US4808407A (en) * | 1987-08-14 | 1989-02-28 | Mooney Chemicals, Inc. | Water-soluble copper salts |
| US6471976B1 (en) | 1990-10-01 | 2002-10-29 | Evelyn J. Taylor | Copper complex bactericide/fungicide and method of making same |
| CA2051716C (en) * | 1990-10-01 | 2002-05-14 | James H. Lefiles | Copper hydroxide dry flowable bactericide/fungicide and method of making and using same |
| ZA931681B (en) * | 1992-04-03 | 1993-12-07 | Griffin Corp | Copper complex bactericide/fungicide and method of making same |
| US5665679A (en) * | 1995-10-18 | 1997-09-09 | Griffin Corporation | Method of desiccating potato vines with copper alkylenediamine |
| EG22120A (en) * | 1999-11-02 | 2002-08-30 | Delta Agro Chemical | Fungicide formulations contain copper and their method for preparation |
| JP4599780B2 (en) * | 2001-09-13 | 2010-12-15 | ダイキン工業株式会社 | Catalyst for producing fluorine-containing alcohol compound and method for producing fluorine-containing alcohol |
| AUPR809001A0 (en) * | 2001-10-04 | 2001-10-25 | Bioacumen Pty Limited | Compositions for the treatment and prevention of plant pathogens |
| AU2002331462B2 (en) * | 2001-10-04 | 2008-01-10 | Bioacumen Pty Limited | Compositions for the treatment and prevention of plant pathogens |
| WO2005036968A1 (en) * | 2003-10-17 | 2005-04-28 | Basf Aktiengesellschaft | Novel copper-containing formulations |
| DE10351004A1 (en) * | 2003-10-30 | 2005-05-25 | Basf Ag | Aqueous nanodispersion-forming formulations of active agents, especially plant protectants such as fungicides, comprise random copolymer of unsaturated sulfonic acid(s) |
| PE20060796A1 (en) | 2004-11-25 | 2006-09-29 | Basf Ag | PROCEDURE TO INTENSIFY THE EFFICIENCY OF ETABOXAM |
| WO2006108835A2 (en) * | 2005-04-15 | 2006-10-19 | Basf Aktiengesellschaft | Use of polylysine in biocide formulations containing copper |
| EP2363421B1 (en) * | 2005-04-18 | 2013-09-18 | Basf Se | Copolymers CP for the preparation of compositions containing at least one type of fungicidal conazole |
| ES2265280B1 (en) * | 2005-06-23 | 2008-03-16 | Universitat Jaume I | APPLICATION OF SHORT CHAIN MONOCARBOXYLL ACIDS FOR THE PROTECTION OF PLANTS AGAINST BIOTIC AND ABIOTIC STRESS. |
| WO2007069767A1 (en) * | 2005-12-16 | 2007-06-21 | Riken | Bactericide for agricultural and horticultural use containing inorganic copper compound as active ingredient |
| US7462227B2 (en) * | 2005-12-30 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Ibuprofen complexes as wood preservatives |
| US7427316B2 (en) * | 2005-12-30 | 2008-09-23 | E.I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
| US7497901B2 (en) | 2005-12-30 | 2009-03-03 | E. I. Dupont De Nemours And Company | Tungstate and molybate wood preservatives |
| US7540906B2 (en) * | 2005-12-30 | 2009-06-02 | E.I. Du Pont De Nemours & Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
| US8192766B2 (en) * | 2006-04-25 | 2012-06-05 | Albaugh, Inc. | Copper-based fungicide/bactericide |
| US8221796B2 (en) | 2006-04-25 | 2012-07-17 | Albaugh, Inc. | Copper-based fungicide/bactericide |
| US9474282B2 (en) * | 2013-12-13 | 2016-10-25 | Tony John Hall | Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses |
| US20150342195A1 (en) * | 2014-06-03 | 2015-12-03 | Myco Sciences Limited | Anti-microbial compositions, preparations, methods, and uses |
| MX2017015797A (en) | 2015-06-08 | 2018-11-09 | Myco Sciences Ltd | Antimicrobial and agrochemical compositions. |
| WO2017112848A1 (en) | 2015-12-23 | 2017-06-29 | American Chemet Corporation | Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby |
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|---|---|---|---|---|
| GB599443A (en) * | 1945-06-01 | 1948-03-12 | Stevensons Dyers Ltd | A new or improved method of rot proofing textile materials |
| GB420533A (en) * | 1932-06-02 | 1934-12-03 | Ig Farbenindustrie Ag | Manufacture of metal salts of polymeric carboxylic acids and the production of shaped articles therefrom |
| GB420589A (en) * | 1933-06-01 | 1934-12-03 | Ig Farbenindustrie Ag | Manufacture of metal salts of polymeric carboxylic acids and the production of shaped articles therefrom |
| GB593416A (en) * | 1943-11-10 | 1947-10-16 | Nuodex Products Co Inc | Improvements in methods of preparing copper fungicide solutions |
| BE484394A (en) * | 1947-08-15 | |||
| FR1590623A (en) * | 1968-06-05 | 1970-04-20 | ||
| SE374686B (en) * | 1971-01-26 | 1975-03-17 | B O Heger | |
| GB1394990A (en) * | 1971-08-12 | 1975-05-21 | Hydrophilics Int Inc | Copolymers and compositions containing copolymers |
| US3900504A (en) * | 1972-02-04 | 1975-08-19 | Mineral Research & Dev Corp | Cuprammonium acetate complex and method of preparing |
| US4020180A (en) * | 1972-02-04 | 1977-04-26 | Mineral Research & Development Corporation | Noncorrosive cuprammonia fungicide and method for using same |
| DE2809244A1 (en) * | 1977-03-04 | 1978-09-21 | Nitto Electric Ind Co | ANTIBACTERIAL AND FUNGICIDAL MATERIAL |
| GB1574939A (en) * | 1977-05-12 | 1980-09-10 | Cuprinol Ltd | Compositions containing preservative metals and their use for the preservation of wood and like materials and as fungicides |
| DE2807293A1 (en) * | 1978-02-21 | 1979-08-23 | Bp Chem Int Ltd | HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEX |
| US4175090A (en) * | 1978-02-23 | 1979-11-20 | Bp Chemicals Limited | Chemical composition |
-
1981
- 1981-04-08 GR GR64628A patent/GR75196B/el unknown
- 1981-04-10 EP EP81102722A patent/EP0039788B1/en not_active Expired
- 1981-04-10 US US06/252,800 patent/US4409358A/en not_active Expired - Lifetime
- 1981-04-10 DE DE8181102722T patent/DE3161008D1/en not_active Expired
- 1981-04-14 IL IL62645A patent/IL62645A/en not_active IP Right Cessation
- 1981-04-14 CA CA000375391A patent/CA1171426A/en not_active Expired
- 1981-04-23 GB GB8112616A patent/GB2077740B/en not_active Expired
- 1981-04-29 MA MA19338A patent/MA19132A1/en unknown
- 1981-04-29 PT PT72950A patent/PT72950B/en not_active IP Right Cessation
- 1981-04-29 IE IE950/81A patent/IE51149B1/en not_active IP Right Cessation
- 1981-04-30 ES ES501820A patent/ES8300003A1/en not_active Expired
- 1981-04-30 BR BR8102689A patent/BR8102689A/en not_active IP Right Cessation
- 1981-04-30 AU AU70015/81A patent/AU538632B2/en not_active Ceased
- 1981-05-01 DK DK194181A patent/DK160910C/en not_active IP Right Cessation
-
1983
- 1983-03-11 US US06/474,309 patent/US4528185A/en not_active Expired - Fee Related
-
1984
- 1984-07-26 KE KE3432A patent/KE3432A/en unknown
-
1986
- 1986-12-30 MY MY469/86A patent/MY8600469A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2077740A (en) | 1981-12-23 |
| EP0039788B1 (en) | 1983-09-28 |
| IL62645A0 (en) | 1981-06-29 |
| BR8102689A (en) | 1982-01-26 |
| EP0039788A3 (en) | 1981-11-25 |
| MA19132A1 (en) | 1981-12-31 |
| ES501820A0 (en) | 1982-10-01 |
| PT72950A (en) | 1981-05-01 |
| AU538632B2 (en) | 1984-08-23 |
| IE810950L (en) | 1981-11-13 |
| DE3161008D1 (en) | 1983-11-03 |
| IL62645A (en) | 1984-04-30 |
| DK160910B (en) | 1991-05-06 |
| AU7001581A (en) | 1981-12-03 |
| IE51149B1 (en) | 1986-10-15 |
| GB2077740B (en) | 1984-04-11 |
| DK194181A (en) | 1981-11-04 |
| MY8600469A (en) | 1986-12-31 |
| ES8300003A1 (en) | 1982-10-01 |
| GR75196B (en) | 1984-07-13 |
| DK160910C (en) | 1991-10-21 |
| PT72950B (en) | 1982-03-26 |
| EP0039788A2 (en) | 1981-11-18 |
| US4409358A (en) | 1983-10-11 |
| KE3432A (en) | 1984-08-17 |
| US4528185A (en) | 1985-07-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |