DE2807293A1 - HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEX - Google Patents
HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEXInfo
- Publication number
- DE2807293A1 DE2807293A1 DE19782807293 DE2807293A DE2807293A1 DE 2807293 A1 DE2807293 A1 DE 2807293A1 DE 19782807293 DE19782807293 DE 19782807293 DE 2807293 A DE2807293 A DE 2807293A DE 2807293 A1 DE2807293 A1 DE 2807293A1
- Authority
- DE
- Germany
- Prior art keywords
- copper
- ammonium
- cuprammonium
- complex
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000007788 liquid Substances 0.000 title claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- OZZOVSQSDIWNIP-UHFFFAOYSA-N acetic acid;azane Chemical compound [NH4+].[NH4+].CC([O-])=O.CC([O-])=O OZZOVSQSDIWNIP-UHFFFAOYSA-N 0.000 claims description 2
- BSXZJWHTFAEYDT-UHFFFAOYSA-N diazanium diformate Chemical compound [NH4+].[NH4+].[O-]C=O.[O-]C=O BSXZJWHTFAEYDT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910000928 Yellow copper Inorganic materials 0.000 claims 1
- 230000002538 fungal effect Effects 0.000 claims 1
- -1 painted surfaces Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 3
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- MKLAGUBOMIFBTR-UHFFFAOYSA-N azane;copper;propanoic acid Chemical compound N.[Cu].CCC(O)=O MKLAGUBOMIFBTR-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000004763 spore germination Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 241000222290 Cladosporium Species 0.000 description 1
- 241001149956 Cladosporium herbarum Species 0.000 description 1
- 241001626940 Coniophora cerebella Species 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241001492222 Epicoccum Species 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000218626 Pinus sylvestris Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 231100000230 acceptable toxicity Toxicity 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000006787 czapek-dox agar Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Materials Engineering (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Description
Homogenes, flüssiges, einen Cuprammonium-komplex Homogeneous, liquid, a cuprammonium complex
umfassendes Präparat Die vorliegende Erfindung bezisht sich auf Präparate, die Cuprammoniumkomplexe von Carbonsäuren enthalten, und auf ein Verfahren zur Herstellung derselben. Comprehensive Preparation The present invention relates to preparations containing cuprammonium complexes of carboxylic acids, and to a process for their preparation the same.
Kupfersalze sind seit langen in fungiziden Präparaten verwendet worden; auch die Toxizität der löslichen Kupfersalze war wahlbekannt. Obgleich es möglich ist, feste Kupferverbindungen mit maßiger und annehmbarer Toxizität herzustellen, ist die Verwendung dieser festen Verbindungen, selbst in sehr feiner Form, aufgrund von Schwierigkeiten uei ihrer einheitlichen Aufbringung auf eine Substratoberfläche, um eine maximale Oberflächenabdekkung zum wirksamen Schutz pro Gewichtseinheit der Verbindung zu erzielen, erheblich eingeschränkt. Sogar wo solche KupFerverbindungen in löslicher Form hergestellt wurden, waren diese Lösungen sehr stark verdünnt mit mehr als 60 Gew.-% Lösungsmittelgehalt pro etwa B % wirksamem Kupfergehalt. Solche Präparate im Zusammenhang mit Cuprawmoniumcarboxylat sind in den US PSS 3 900 504 und 4 020 180 beschrieben worden. Solche Lösungen ergeben ein anderes Problem, nämlich die Handhabung großer Massen, die sie wirtschaftlich unattraktiv macht, und weiter bewirkt die begrenzte Löslichkeit dieser Komplexe zusätzliche Probleme aufgrund von Ausfällung und Sedimentation in den zum Transport verwendeten Behältern. Beim großtechnischen Betrieb kann diese Aus fällung auch zur Blockierung von Pump- und Sprühuorrichtungen führen.Copper salts have long been used in fungicidal preparations; the toxicity of the soluble copper salts was also known. Although it is possible is to produce solid copper compounds with moderate and acceptable toxicity, is due to the use of these solid compounds, even in very fine forms difficulties in applying them uniformly to a substrate surface, a maximum surface coverage for effective protection per unit weight of the Achieve connection, severely limited. Even where such copper connections were prepared in soluble form, these solutions were very dilute with greater than 60% by weight solvent content per about B% effective copper content. Such Preparations related to cupra monium carboxylate are in the US PSS 3 900 504 and 4020 180. Such solutions give another problem, namely the handling of large masses, which makes them economically unattractive, and further, the limited solubility of these complexes creates additional problems due to precipitation and sedimentation in the containers used for transport. In large-scale operations, this precipitate can also block pumping and lead spray devices.
Es wurde nun gefunden, daß man homogene wässrige Lösungen von Cuprammoniumkomplexen herstellen kann, die nicht nur relativ geringere Lösungsmittelmengen enthalten, sondern auch einen höheren, wirksamen Kupfergehalt als bisher aufweisen.It has now been found that homogeneous aqueous solutions of cuprammonium complexes can be obtained can produce that not only contain relatively small amounts of solvent, but also have a higher, more effective copper content than before.
Die vorliegende Erfindung bezieht sich somit auf ein homogenes flüssiges Präparat aus einem Cuprammoniumkomplex aus einer oder mehreren C1,4 Monocarbonsäuren mit zwischen 4 und 10 Gew.-% gelöstem Kupfer und bis zu 40 Gew.-% Wasser.The present invention thus relates to a homogeneous liquid Preparation from a cuprammonium complex of one or more C1.4 monocarboxylic acids with between 4 and 10% by weight of dissolved copper and up to 40% by weight of water.
In einer weiteren Ausführungsform richtet sich die vorliegende Erfindung auf ein Verfahren zur Herstellung eines homogenen, flüssigen Präparates aus einem Cuprammoniumkomplex aus einer oder mehreren C14 Monocarbonsäuren mit zwischen 4 und 10 (;ew. - gelöstem Kupfer und bis zu 40 Gew.-% Wasser, das dadurch gekennzeichnet ist, daß man ein saures Ammoniumsalz der Monocarbonsäure mit einer Kupferverbindung aus der Gruppe von Cupro- und Cuprioxid in Anwesenheit von wässrigem Ammonium umsetzt.The present invention is directed in another embodiment to a process for the production of a homogeneous, liquid preparation from a Cuprammonium complex of one or more C14 monocarboxylic acids with between 4 and 10 (; ew. - dissolved copper and up to 40 wt .-% water, which is characterized is that you have an acidic ammonium salt of the monocarboxylic acid with a copper compound from the group of cuprous and cupric oxide converts in the presence of aqueous ammonium.
er Monocarbonsäureteil im Salz kann von gesättigten oder ungesättigten Monocarbonsäuren hergeleitet werden. Solche Säuren sind z.l. Iimeiscn, Essig-, Propionsäure, die isomeren Buttersäuren, Acryl- und Methacrylsäure. Die hier verwendete Bezeichnung "saures Ammoniumsalz" bezieht sich auf Salze, in weichen 2 Mol des Säuretells pro Mol Ammoniumion, auf chemischer Squivalenzgrundlage, anwesend sind. So sfi--1d die sauren Ammoniumsalze z.fl. Ammoniumdiformiat, Amnon iumdiacetat und/oder Ammoniumdipropionat. Das Produkt aus der Reaktion zwischen dem sauren Ammoniumsalz und dem Kupferoxid in Anwesenheit von wässrigen Ammoniak ist eine dunkelblaue wässrige Lösung, die den Cuprammoniumkomplex in einer Konzentration im angegebenen Bereich enthält.The monocarboxylic acid part in the salt can be saturated or unsaturated Monocarboxylic acids are derived. Such acids are z.l. Iimeiscn, acetic, propionic acid, the isomeric butyric acids, acrylic and methacrylic acid. The term used here "Acid ammonium salt" refers to salts in which 2 moles of the acid part per Moles of ammonium ion, on a chemical equivalence basis, are present. So sfi - 1d the acidic ammonium salts z.fl. Ammonium diformate, ammonium diacetate and / or ammonium dipropionate. The product of the reaction between the acidic ammonium salt and the copper oxide in the presence of aqueous ammonia is a dark blue aqueous solution which contains the cuprammonium complex in a concentration in the specified range.
Die erfindungsgemäßen, flüssigen Präparate naben aufgrund der Anwesenheit von Kupfer fungizide Aktivität, sl finden daher häufig Verwendung, z.B. als Farbbiozide, Holzkonservierungsmittel, Fungizide zur Verhütung von Mehltau auf Textilien und zur Bekämpfung von nlgsn und Meeresschmutz. Die Präparate inhibieren insbesondere das Wachstum der rungi Cladosporium herbarum, die für das Verderben von Farben Verantwortlich sind, und Coniophora cerebella, die den Abbau von Holz bewirken.The liquid preparations according to the invention have due to their presence fungicidal activity of copper, sl are therefore often used, e.g. as color biocides, Wood preservatives, fungicides for the prevention of powdery mildew on textiles and to combat nlgsn and marine pollution. In particular, the preparations inhibit the growth of the rungi Cladosporium herbarum, responsible for the spoilage of colors and Coniophora cerebella, which cause wood to break down.
Für die obigen Zwecke können die Präparate als solche in Form ihrer wässrigen Lösung verwendet werden. Eis wässrige Lösung kann jedoch andere übliche Zusätze enthalten, die ihre Aktivität ergänzen, wie freie Ameisensäure, Propionsäure, Formalin und Bisulfite. Weiterhin können die wässrigen Lösungen Netzmittel, Mittel zum besseren Verbreiten oder Klebemittel enthalten oder notwendigenfalis mit Mineralölen emulgiert werden.For the above purposes, the preparations as such can be used in the form of their aqueous solution can be used. However, ice aqueous solution can be other usual Contain additives that complement their activity, such as free formic acid, propionic acid, Formalin and bisulfites. The aqueous solutions can furthermore contain wetting agents, agents for better spreading or containing adhesives or, if necessary, with mineral oils be emulsified.
Die Konzentration des auf das Substrat aufgebrachten Cuprammoniumkomplexe hängt nicht nur vom Substrat und dessen Endverwendung sonden auch von der Natur des zu behandelnden oder zu verhindernden Befalls ab; sie kann jedoch vom Fachmann leicht bestimmt werden. So kann z.B. zur Holzkonservierung eine Bchandlung mit Kupferkonzentrationen zwischen 0,4-1,0 % verwendet werden.The concentration of the cuprammonium complex applied to the substrate depends not only on the substrate and its end use probes also on nature the infestation to be treated or prevented; however, it can be done by a person skilled in the art can be easily determined. For example, a treatment with copper concentrations can be used to preserve wood between 0.4-1.0% can be used.
Wo es zweckmäßig ist, die Cuprammoniumkomplexlösung zur Aufbringung hoher Volumen zu verdünnen, wie z.B. ei der oben genannten Holz-konservierung, erfolgt die Verdünnung vorzugsweise unter Verwendung einer 1,3-%igen wassrigen Ammoniaklösung, um die Ausfäl lung des Komplexes zu verhindern. Wird nur Wasser als Verdünnungs mitte3 verwendet, z B. bei Verdünnungen von etwa 1 100:1, kann sich ein flockiger, gelatinöser, blauer Niederschlag abtrennen.Where appropriate, the cuprammonium complex solution for application high volume, such as the above-mentioned wood preservation, is carried out the dilution preferably using a 1.3% aqueous ammonia solution, to prevent the complex from precipitating. Only uses water as a dilution middle3 used, e.g. at dilutions of about 1 100: 1, a flaky, Separate gelatinous, blue precipitate.
Die erfindungsgemäßen Cuprammoniumkomplnxe haben in Wasser eine größere Löslichkeit als die üblichen Kupfersalze, wie Kupferfor-4niat und Kupferpropionat, und zeigen nach ihrer Herstellung einen pH-Wert zwischen 7 und 9. Ihre verbesserte Löslichkeit ermöglicht ein freieres Fließen und eine gleichmäßigere Verteilung des Präparates auf dem Substrat, insbesondere bei Verwendung als Spray.The cuprammonium complexes according to the invention have a larger concentration in water Solubility than the usual copper salts, such as copper formate and copper propionate, and after their production show a pH value between 7 and 9. Their improved Solubility enables more free flow and more even distribution of the Preparation on the substrate, especially when used as a spray.
Wie aus der Tabelle ersichtlich, sind die Cuprammoniumkomplexe im Vergleich zu Kuppferpropionat und -formiat stärker wasserlöslich, was die Aufbringung durch Sprühen erleichtert. Die unterschiedlichen Kupferlöslichkeiten (bei Zimmertemperatur) sind wie folgt: Verbindung % Cu in einer gesättigten wässrigen Lösung Kupferpropionat 2,2 Cuprammoniumpropionatkomplex 5-10,0 Kupferformiat 2,9 Cuprammoniumformiatkomplex 4,5 Die folgenden Beispiele veranschaulichen die vorliegende Erfinding, ohne sie zu beschränken.As can be seen from the table, the cuprammonium complexes are im Compared to copper propionate and copper formate more soluble in water, which makes the application relieved by spraying. The different copper solubilities (at room temperature) are as follows: Compound% Cu in a saturated aqueous solution Copper propionate 2.2 cuprammonium propionate complex 5-10.0 copper formate 2.9 cuprammonium formate complex 4.5 The following examples illustrate the present invention without it to restrict.
B e i s p i e l e A. Herstellung dar Komplexe Der Komplex kann durch Reaktion des sauren Ammoniumsalzes (70 , Gew./Gew. wässrige Lösung) mit Cupri- oder Cuprooxid und wässrigem Ammoniak hergestellt werden. Einige Herstellungen sind unten beschrieben.EXAMPLE A. Preparation of the complexes The complex can be produced by Reaction of the acidic ammonium salt (70, w / w aqueous solution) with cupric or Cuprous oxide and aqueous ammonia can be produced. Some fabrications are below described.
Cuprammmoniumpropionatkomplex 1. 212 g einer 70-%igen wässrigen Lösung aus Ammoniumdipropionat wurden zu 30 g Cuprioxid zugefügt und die Mischung 30 Minuten zum Rückfluß erhitzt. Nach dem Abkühlen wurden 88 g wässriger Ammoniak (33,3 % Gew./Gew. NH3) zugefügt und die Mischung zu einer dunkelblauen Lösung filtriert, die 13,5 % Gew./Gew. NH3, 39,8 % Gew./Gew. Propionat, 7,0 % Gew./Gew. Kupfer und 39,7 % Gew./Gew. Wasser enthielt (pH = 8,0).Cuprammonium propionate complex 1. 212 g of a 70% strength aqueous solution of ammonium dipropionate was added to 30 g of cupric oxide and the mixture for 30 minutes heated to reflux. After cooling, 88 g of aqueous ammonia (33.3% w / w. NH3) was added and the mixture filtered to a dark blue solution, the 13.5 % W / w NH3, 39.8% w / w Propionate, 7.0% w / w Copper and 39.7% w / w Contained water (pH = 8.0).
2. 106 g einer 70-%igen wässrigen Lösung aus Ammoniumdipropionat wurden zu 30 g Cuprioxid zugefügt und die Mischung 30 Minuten zum Rückfluß erhitzt. Nach dem Abkühlen wurden 44 g wässriger Ammoniak (33,3 % NH3) zugefügt, die Lösung erneut abgekühlt und zur Entfernung von nicht umgesetztem Cuprioxid (6,6 g) Filtriert Die endgültige Lösung enthielt 13,0 % Gew./Gew. NH3, 38,2 d Gew./Gew. Propionat, 10 % Gew./Gew. Kupfer und 38,8 % Gew./Gew.2. 106 g of a 70% strength aqueous solution of ammonium dipropionate were made added to 30 g of cupric oxide and the mixture heated to reflux for 30 minutes. To 44 g of aqueous ammonia (33.3% NH3) were added to the cooling process, and the solution was again added cooled and filtered to remove unreacted cupric oxide (6.6 g) final solution contained 13.0% w / w. NH3, 38.2 d w / w Propionate, 10 % W / w Copper and 38.8% w / w.
Wasser (pH = 8,0 3. 212 g einer 70-%igen wässrigen Lösung aus Ammoniumdipropionat wurden zu 30 9 Cuprooxid zugefügt und 1 Stunde zum Rückfluß erhitzt. Nach dem Abkühlen wurden 88 g wässriger Ammoniak (33,3 ,«) zugefügt, die Lösung wurde abgekühlt und zur Entfernung von überschüssigem metallischem Kupfer (12 g) filtriert. Die endgültige Lösung enthielt 14,0 % Gew./Gew. NH3, 41,3 % Gew./Gew. Proionat, 5,0 % Gew./Gew. Kupfer und 39,7 % Gew./Gew. Wasser (pH = 7,6).Water (pH = 8.0 3. 212 g of a 70% strength aqueous Solution of ammonium dipropionate were added to 30 9 cuprous oxide and 1 hour for Heated to reflux. After cooling, 88 g of aqueous ammonia (33.3, «) were added, the solution was cooled and used to remove excess metallic copper (12 g) filtered. The final solution was 14.0% w / w. NH3, 41.3% w / w Proionate, 5.0% w / w Copper and 39.7% w / w Water (pH = 7.6).
Cuprammoniumformiatkomplex 4. Dieser Komplex wurde durch Umsetzung von Cuprioxid mit wässrigem Ammoniak und 70-%igem wässrigem Ammoniumformiat hergestellt. Die endgültige Lösung enthielt 4,5 Gew.- Kupfer, 40 Gew.-% Formiat und 39,0 Gew.- Wasser.Cuprammonium formate complex 4. This complex was made by reaction made of cuprioxide with aqueous ammonia and 70% aqueous ammonium formate. The final solution contained 4.5 wt% copper, 40 wt% formate and 39.0 wt% Water.
8. Aktivität der Cuprammoniumkomplexe Holzkonserierungsaktivität 5. Der gelöste Komplex wurde hei verschiedenen Verdünnungen auf Blöcke von Sco Fichtensplintholz der Art Pinus sylvestris wie folgt aufgebracht.8. Activity of cuprammonium complexes wood preservation activity 5. The dissolved complex was applied to blocks of spruce sapwood at various dilutions of the species Pinus sylvestris applied as follows.
Die Blöcke wurden ofengetrocknet, gewogen und mit einer Lösung aus Cuprammoniumpropionat vakuumimprä3niert. Fs wurden 12 Blöcke mit jeder der folgenden Konzentrationen des gelösten Komplexes (berechnet als % Kupfer) behandelt: 1,0, 0,63, 0,40, 0,25, 0,16, 0,10 und 0,063. Die so behandelten Blöcke wurden zusammen mit unbehandelten Blöcken einer Kultur des Organismus Coniphora cerebella 6 Wochen in Erde enthaltenden Flaschen ausgesetzt.The blocks were oven dried, weighed and made with a solution Cuprammonium propionate vacuum impregnated. Fs were 12 blocks with each of the following Concentrations of the dissolved complex (calculated as% copper) treated: 1.0, 0.63, 0.40, 0.25, 0.16, 0.10 and 0.063. The blocks so treated were put together with untreated blocks of a culture of the organism Coniphora cerebella for 6 weeks exposed in bottles containing soil.
Nach dieser Zeit wurden die Testblücke aus der Kultur entfernt, gewogen, ofengetrocknet und erneut gewogen. Die endgültige, ofengetrocknete Masse wurde mit der anfänglichen trockenen Masse verglichen, um den Massenverlust aufgrund der Zersetzung durch den Organismus zu berechnen. Weiter wurden 2 mit jeder Konzentration behandelte, und dem Organismus nicht ausgesetzte Blöcke ofengetrocknet und gewogen, um die Aufnahme des Konservierungskomplexes zu berücksichtigen.After this time, the test blocks were removed from the culture, weighed, oven dried and weighed again. The final, oven-dried mass was made with the initial dry mass compared to the mass loss due to the decomposition by the organism. Next were 2 with each Concentration treated and oven-dried blocks not exposed to the organism and weighed to take into account the intake of the preservation complex.
Auf der Basis des Gewichtsverlustes betrug der toxische Grenzwert, d.Ii. die Spanne zwischen derjenigen Konzentration, die gerade noch cine Zersetzung zuließ, und der nächst höheren Konzentration in der Reihe, die die ZcNsetzung insgesamt inhibiert, 0,25-0,40 o Kupfer in der Behandlungslösung. Die Holzbeladung, ausgedrückt als Kupfer, für diesen toxischen Grenzwert beträgt 1,9-3,2 kg/m3 Hclz.On the basis of weight loss, the toxic limit was d.Ii. the range between that concentration which just barely cine decomposition admitted, and the next higher concentration in the series, which the total decomposition inhibited, 0.25-0.40 o copper in the treatment solution. The wood loading, expressed than copper, for this toxic limit value is 1.9-3.2 kg / m3 Hclz.
Zum weiteren Vergleich wurde eines der am häufigsten verwendeten, in Wasser verdünnten Konservierungsmittel auf der Rasis von Kupfersulfat, Kaliumdichromat und Arsenpentoxid, das als CCA Perservative" bekannt ist, unter Verwendung derselben Holzblöcke und desselben Organismus getestet. Dies ergab einen toxischen Grenzwert von 1,8-3,0 kg/m3, ausgedrückt als Metallgehalt. Bei einer ähnlichen Metallbeladung wie im Fall von CCA erlaubt die vorliegende Erfindung somit die Verwendung der günstigeren Kupferkomplexe.For further comparison, one of the most frequently used, Preservatives diluted in water based on copper sulfate, potassium dichromate and arsenic pentoxide known as CCA Perservative using the same Blocks of wood and the same organism tested. This resulted in a toxic limit value from 1.8-3.0 kg / m3, expressed as metal content. With a similar metal load thus, as in the case of CCA, the present invention allows the use of the cheaper ones Copper complexes.
Farbbiozidakt ivität 6. Die Aktivität von Kupferammoniumpropionat als Farbbiozid wurde wie folgt ausgewertet: 500 ppm Kupferammoniumpropionat wurden zu einem geschmolzenen Medium (50°C) aus Czapek Dox Agar (Oxid CM 97) zugefügt, in 100 mm Petrischalen gegossen, und die Mischung wurde härten gelassen.Color biocidal activity 6. The activity of copper ammonium propionate as a color biocide was evaluated as follows: 500 ppm copper ammonium propionate were added to a molten medium (50 ° C) made of Czapek Dox agar (Oxid CM 97), poured into 100 mm petri dishes and the mixture was allowed to harden.
Die oberflächenfeuchtigkeit wurde vom Wachstumsmedium durch Trocknon bei 50°C. entfernt. Die Agarplatten wurden mit den Suspensionen der Testorganismen unter Verwendung eines Mehrpunktinkulators beimpft und 7 Tage bei 2r;OC. bebrütet. Es wurde ein entsprechendes Kontrollmedium ohne Zugabe des Komplexes hergestellt, beimpft und unter identischen Bedingungen bebrütet. Man erhielt die folgenden Ergebnisse einer Sporenkeimung. In allen Fällen wurde selbst das leichteste Wachstum oder eine Sporenkeimung als Versagen des Konservierungsmittels beim Inhibieren des Organismus angesehen.The surface moisture was determined by drying on the growth medium at 50 ° C. removed. The agar plates were filled with the suspensions of the test organisms inoculated using a multipoint accumulator and 7 days at 2r; OC. incubated. A corresponding control medium was prepared without adding the complex, inoculated and incubated under identical conditions. The following results were obtained a spore germination. In all cases there was even the slightest growth or one Spore germination as failure of the preservative to inhibit the organism viewed.
Cladosporium Fusarium Penicillium Pestaherbarum species expansum
lotia macrotricha
Claims (4)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782807293 DE2807293A1 (en) | 1978-02-21 | 1978-02-21 | HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEX |
| FR7805392A FR2417943A1 (en) | 1978-02-21 | 1978-02-24 | Biocidal copper-contg. liq. compsns. - contg. cuprammonium complex of mono:carboxylic acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782807293 DE2807293A1 (en) | 1978-02-21 | 1978-02-21 | HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEX |
| FR7805392A FR2417943A1 (en) | 1978-02-21 | 1978-02-24 | Biocidal copper-contg. liq. compsns. - contg. cuprammonium complex of mono:carboxylic acid |
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| Publication Number | Publication Date |
|---|---|
| DE2807293A1 true DE2807293A1 (en) | 1979-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| DE19782807293 Ceased DE2807293A1 (en) | 1978-02-21 | 1978-02-21 | HOMOGENOUS, LIQUID, PREPARATION COMPRISING A CUPRAMMONIUM COMPLEX |
Country Status (2)
| Country | Link |
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| DE (1) | DE2807293A1 (en) |
| FR (1) | FR2417943A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039788A2 (en) * | 1980-05-03 | 1981-11-18 | BASF Aktiengesellschaft | Copper complexes, their preparation, their use in controlling plant pests and agents therefor |
| DE3805428A1 (en) * | 1987-10-17 | 1989-08-31 | Hoelter Heinz | Bactericidal and fungicidal wallpaper adhesive |
| WO2015185994A1 (en) * | 2014-06-03 | 2015-12-10 | Myco Sciences Limited | Anti-microbial compositions, preparations, methods, and uses |
| EP2934131A4 (en) * | 2012-12-18 | 2016-06-22 | Kemin Ind Inc | Compositions for the control of algae in commercial horticulture |
| EP3079476A4 (en) * | 2013-12-13 | 2017-08-23 | Myco Sciences Limited | Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses |
| US11395492B2 (en) | 2015-06-08 | 2022-07-26 | Vm Agritech Limited | Antimicrobial and agrochemical compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2051716C (en) * | 1990-10-01 | 2002-05-14 | James H. Lefiles | Copper hydroxide dry flowable bactericide/fungicide and method of making and using same |
| US6471976B1 (en) | 1990-10-01 | 2002-10-29 | Evelyn J. Taylor | Copper complex bactericide/fungicide and method of making same |
| ZA931681B (en) * | 1992-04-03 | 1993-12-07 | Griffin Corp | Copper complex bactericide/fungicide and method of making same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1505388A (en) * | 1975-11-27 | 1978-03-30 | Bp Chem Int Ltd | Acid salt solutions |
-
1978
- 1978-02-21 DE DE19782807293 patent/DE2807293A1/en not_active Ceased
- 1978-02-24 FR FR7805392A patent/FR2417943A1/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039788A2 (en) * | 1980-05-03 | 1981-11-18 | BASF Aktiengesellschaft | Copper complexes, their preparation, their use in controlling plant pests and agents therefor |
| EP0039788A3 (en) * | 1980-05-03 | 1981-11-25 | Basf Aktiengesellschaft | Copper complexes, their preparation, their use in controlling plant pests and agents therefor |
| DE3805428A1 (en) * | 1987-10-17 | 1989-08-31 | Hoelter Heinz | Bactericidal and fungicidal wallpaper adhesive |
| EP2934131A4 (en) * | 2012-12-18 | 2016-06-22 | Kemin Ind Inc | Compositions for the control of algae in commercial horticulture |
| EP3079476A4 (en) * | 2013-12-13 | 2017-08-23 | Myco Sciences Limited | Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses |
| US10729139B2 (en) | 2013-12-13 | 2020-08-04 | Myco Sciences Limited | Acid-solubilized copper-ammonium complexes and copper-zinc ammonium complexes, compositions, preparations, methods, and uses |
| EP4074318A1 (en) * | 2013-12-13 | 2022-10-19 | VM Agritech Limited | Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses |
| WO2015185994A1 (en) * | 2014-06-03 | 2015-12-10 | Myco Sciences Limited | Anti-microbial compositions, preparations, methods, and uses |
| US11395492B2 (en) | 2015-06-08 | 2022-07-26 | Vm Agritech Limited | Antimicrobial and agrochemical compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2417943B1 (en) | 1984-08-10 |
| FR2417943A1 (en) | 1979-09-21 |
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