EP0368956A1 - Quaternary ammonium dithiocarbamate compounds - Google Patents
Quaternary ammonium dithiocarbamate compoundsInfo
- Publication number
- EP0368956A1 EP0368956A1 EP89905248A EP89905248A EP0368956A1 EP 0368956 A1 EP0368956 A1 EP 0368956A1 EP 89905248 A EP89905248 A EP 89905248A EP 89905248 A EP89905248 A EP 89905248A EP 0368956 A1 EP0368956 A1 EP 0368956A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- carbon atoms
- water
- alkyl
- compound according
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- 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
- A01N37/18—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 containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/20—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 containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/44—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a carbon atom of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2425—Thiocarbonic acids and derivatives thereof, e.g. xanthates; Thiocarbamic acids or derivatives thereof, e.g. dithio-carbamates; Thiurams
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Definitions
- the present invention relates to novel surfactant compounds and more specifically it relates to novel intermolecular quaternary ammonium dithiocarbamate compounds having particularly valuable surfactant properties, as well as other properties and advantages providing applications to a wide variety of commercial areas.
- Dithiocarbamates are known microbicidal agents useful in industrial applications and recently in plant protection.
- one particularly valuable microbicidal product that has been on the market for many years is a combination of equal parts by weight of sodium dimethyldithiocarbamate and disodium ethylene bis-dithiocarbamate (30%, by weight, total active ingredients).
- This material is used in many industries for controlling the growth of bacteria, yeast and fungi, such as those found in industrial recirculating water cooling towers, air washers, evaporative condensers, pulp and paper mills, drilling fluids, secondary and tertiary petroleum recovery, cane and beet sugar mills, and the like.
- This compound has also been used for controlling the growth of algae in some of these applications.
- dithiocarbamate compounds such as disodium ethylene bis-dithiocarbamate or sodium dimethyl- dithiocarbamate, have no surface active properties. These compounds are not wetting or spreading agents, are insoluble in oil or hydrocarbons, and are incapable of emulsifying water or solubilizing waterinsoluble organic compounds. These compounds are dried with considerable difficulty, and are characterized by a noxious odor.
- a family of novel surfactant compounds are characterized by the general formula I or II:
- R 1 and R 2 are the same or different and are selected from the group consisting of alkyl groups containing from 1 to 23 carbon atoms, optionally interrupted by one or more of the groups
- R 5 is H or CH 3 and n is 1 to about 75, and R 6 and R 7 are the same or different and are selected from the group consisting of alkyl containing from 1 to 10 carbon atoms, hydroxyethyl, hydroxypropyl, or benzyl;
- R 3 is R 1 , B 2 or R 4 ;
- R 4 is the residue from a quaternizing agent selected from the group consisting of a benzyl or C 1 to C 10 alkyl halide or a dimethyl or diethyl sulfate; or where R 17 R 3 , R 6 and R 7 together form a cyclic moiety containing from 3 to 5 carbon atoms, optionally interrupted by 1 or 2 atoms selected from O or N; and optionally substituted by one or more alkyl groups containing 1 to 6 carbon atoms;
- R 8 and R 9 are the same or different and are selected from the group consisting of an alkyl group and containing from 1 to 4 carbon atoms;
- A is an alkylene chain containing from 2 to 10 carbon atoms.
- Another aspect of the present invention provides a method for preparing the novel compounds described above.
- the steps of this method include mixing, in a solvent or fluidizing liquid, a quaternary ammonium compound having the formula
- R 1 , R 2 , R 3 and R 4 are as defined above and X is an appropriate anion, with an alkali metal dithiocarbamate salt having the formula
- R 8 , R 9 and A are as defined above and M is a cation.
- a chemical reaction occurs upon mixture and produces a largely organic rich phase containing most of the product and a largely aqueous phase containing most of the salt MX.
- the preparation is continued by separating the phases and recovering the organic phase containing the novel quaternary ammonium dithiocarbamate.
- compositions employing the novel compounds of the invention containing as the active ingredient one or more of the novel compounds of the present invention, as surfactants, microbiocides, e.g., fungicides, algacides. bactericides, and lubricity additives, fuel oil additives, emulsifiers, and wood and paper preservatives.
- surfactants e.g., fungicides, algacides. bactericides, and lubricity additives, fuel oil additives, emulsifiers, and wood and paper preservatives.
- Novel quaternary ammonium alkyl dithiocarbamate salts are described which are characterized by surfactant properties, including surface and interfacial tension lowering and emulsification. These compounds may also be useful as antimicrobial agents, lubricity additives, wood preservatives, household cleaners and metal deactivators, or active ingredients in such compositions.
- R 1 and R 2 are the same or different and are selected from the group consisting of alkyl groups containing from 1 to
- R 5 is H or CH 3 and n is 1 to about 75, and R 6 and R 7 are the same or different and are selected from the group consisting of alkyl containing from 1 to 10 carbon atoms, hydroxyethyl, hydroxypropyl, or benzyl;
- R 3 is R 1 , R 2 or R 4 ;
- R 4 is the residue from a quaternizing agent selected from the group consisting of a benzyl or C 1 to C 10 alkyl halide or a dimethyl or diethyl sulfate; or where R 1 , R 3 , R 6 and R 7 together form a cyclic moiety containing from 3 to 5 carbon atoms, optionally interrupted by 1 or 2 atoms selected from O or N; and optionally substituted by one or more alkyl groups containing 1 to 6 carbon atoms;
- R 8 and R 9 are the same or different and are selected from the group consisting of an alkyl containing from 1 to 4 carbon atoms; and A is an alkylene chain containing from 2 to 10 carbon atoms.
- the maximum number of quaternary ammonium moieties present in each molecule of compound according to the present invention is four.
- One exemplary class of compounds according to the present invention are quaternary ammonium diethyldithio-carbamates, i.e., where R 8 and R 9 in formula I above are ethyl groups.
- this class are C 12 - C 16 alkyl dimethyl- benzyl ammonium diethyldithiocarbamate, dioctyldimethyl ammonium diethyldithiocarbamate, and didecyldimethyl ammonium diethyldithiocarbamate.
- Another exemplary class of compounds are quaternary ammonium ethylene bisdithiocarbamates, characterized by formula II, in which A is an ethylene group.
- a specific example of this latter class is alkyl dimethylbenzyl diammonium ethylene bisdithiocarbamate.
- Quaternary ammonium compound reactants employed in the present method may desirably contain at least one methyl group and preferably at least two methyl groups, i.e. where one or two of R 1 through R 4 on the ammonium nitrogen atom are methyl.
- Other desirable R groups are benzyl, or alkyl groups containing from 1 to 18 carbon atoms, preferably from about 8 to about 18 carbon atoms.
- the source of the latter long-chain alkyl group will often be a mixture of fatty compounds, and this substituent will be designated by a range of carbon atoms for the chain, for example C 10 -C 15 , or C 12 -C 18 .
- a substituent on the quaternary ammonium nitrogen may be a fatty amido, or fatty ester group, or it may include an ether chain from alkylene oxide groups.
- Suitable aryl R groups are phenyl, lower alkyl-substituted benzyl and/or halogenated benzyl.
- Desired quaternary ammonium compounds for use in this preparative method may be formed by quaternizing any tertiary amine by conventional means with convenient quaternizing agents.
- ethylene and propylene oxide conveniently convert primary and secondary amines to tertiary amines, which may be quaternized.
- Desirable commercially available tertiary amines for quaternization include the octyl, decyl, dodecyl, C 14 , C 16 and C 18 alkyl dimethyl amines, mixtures thereof and dioctyl and didecyl methyl amines [Ethyl Corp].
- Other commercially available materials for forming the quaternary ammonium compounds are coco (C 8 C 10 C 12 C 14 mixtures) dimethyl and dihydroxyethyl (RN(CH 2 CH 2 OH) 2 and C 14 , C 16 ,C 18 dimethyl and dihydroxy ethyl and dihydroxypropyl amines [AKZO Chemie and Sherex].
- Imidazolines and their corresponding quaternary derivatives can also be employed to make a desired quaternary ammonium compound from a variety of alkyl carboxylic acids, and are represented by the formula:
- R 1 is the alkyl of a carboxylic acid of 1 to 21 carbon atoms
- R 2 is hydroxyethyl, hydroxy propyl, or the residue from a higher alkylepoxide
- R 3 is the residue from a quaternizing agent including benzyl, methyl, butyl, decyl
- X is a halide or sulfate ion.
- Amino amides are another important class of amines which are readily quatemized and conveniently converted by the process described below to dithiocarbamate salts of the present invention. They can be represented by the formula:
- R 1 is as above and R 2 is R 1 or the residue from a different carboxylic acid.
- Alkylation by an epoxide or by an alkyl halide or sulfate followed by quaternization provides a quaternary ammonium compound for use in this invention for conversion to a new surface active dithiocarbamate compound.
- the imidazoline and amino amide functions are frequently produced in the same molecule.
- Amides of dimethylaminopropyl amine are an important raw material from which quaternary ammonium dithiocarbamates can also be readily made. These compounds have the formula:
- R 1 and R 3 are as above, R 4 and R 5 are each the same or a different R 3 .
- R 4 and R 5 are each the same or a different R 3 .
- trialkyl amines with 12 to 30 carbon atoms in which all 3 alkyls are essentially equal are an important group of compounds which, when quaternized and reacted with a dithiocarbamate according to this invention make products with unusual solubility and surface active properties.
- Such quaternary ammonium cations are commercially available, e.g., tetrabutyl ammonium, tributylmethylammonium [Ethyl], tricaprylmethyl ammonium and triC 8 - 10 alkyl methyl [Henkel].
- alkylpyridines and pyridine are another important source of tertiary amines for quaternary ammonium compounds useful in this invention.
- One preferred source are the still residues from the production (from acetaldehyde and ammonia) of aldehyde collidine or 2-methyl-5-ethylpyridine and similar products which are crude mixtures of alkylpolypyridines [Lonza]. These are conveniently quaternized with benzylchloride.
- their dithiocarbamate salts are extremely insoluble and make excellent corrosion inhibitors. They typically contain from 2 to 4 pyridine residues in each molecule.
- Another group of multifunctional quaternary ammonium dithiocarbamates are based on the amines resulting from successive cyanoethylation and reduction of alkylamines. Particularly preferred is
- R is C 18 from tallow.
- Polyether amines are another useful source of tertiary amines from which to make preferred products of this invention and are represented by the structure:
- amines also include
- n 1.5 to 15 and can be readily made from the commercially avaialable primary amines [Texaco Corp.] by methylating with methyl chloride plus an equal (molar) amount of sodium hydroxide.
- Other ether amines and ether diamines include C 8 to C 20 alcohol derivatives [Jetco] having the formula:
- Another amine which forms a desirable quaternary ammonium compound of the invention is represented by:
- R 1 is poly (2 or more) functional polyol and n is equal to the number of hydroxyl groups.
- These amines which do not contain a hydrocarbon hydrophobe are also commercially available [Texaco's Jeffamines].
- R 7 is an alkyl of 2 to 6 carbon atoms, and is commerically available [e.g., Quadrol, BASF].
- Convenient quaternizing agents useful for converting the tertiary amines cited above to quaternary ammonium compounds are: methyl, ethyl, butyl and benzyl chloride, dimethyl and diethyl sulfate; and other agents well known in the art. Most useful are methyl chloride, dimethyl sulfate and benzyl chloride.
- the X in the quaternary ammonium compound is preferably Cl-' but may also be any other appropriate anion, such as an anion of a mineral acid, e.g., Br-, SO 4 -2 and the like.
- the dithiocarbamate reactant of the present inventive method is a dithiocarbamate salt, as represented by the formula
- R 8 and R 9 are hydrogen or short chain alkyl groups containing from 1 to about 4 carbon atoms.
- R 8 and R 9 may be H and CH 3 , H and C 2 H 5 , CH 3 and CH 3 , or C 2 H 5 and C 2 H 5 , respectively.
- A is -CH 2 -CH 2 -.
- M is preferably an alkali metal cation, such as sodium, potassium, lithium or calcium. However, M may be another appropriate cation, such as NH 4 +, alkyl ammonium or the like.
- the compounds of the present invention when produced according to the described method do not rely on a simple mixing of two components. Rather, the reaction of the components causes a concentrated end product containing reduced salt content.
- the reaction takes place under ambient temperature conditions with no significant exotherm so that neither heating nor cooling is required. This does not exclude either lowered temperatures, as down to about 10 C, or elevated temperatures, as up to about 40 C. Agitation is required during the reaction, and conventional stirring or mixing means may be employed.
- the reaction medium is a solvent or fluidizing liquid which will permit easy and efficient mixing of the reactants.
- the reaction medium may therefore be the solvents in which the reactants are prepared, i.e. generally water for the dithiocarbamate reactant, and water and a lower alcohol for the quaternary ammonium reactant.
- the proportions of reactants employed in the preparative method for the compounds of the invention may vary appreciably from the stoichiometric ratios. It is advantageous to use either the dithiocarbamate or the quaternary ammonium compound in excess of stoichiometry to ensure sufficient distribution of the dithiocarbamate salt to the largely organic phase. A typical excess of dithiocarbamate over quaternary reactant, or vice versa, is 20%.
- the concentration of the reactants in the form in which they are charged to the reaction medium may vary widely. It is generally most convenient to use the reactants at the concentrations at which they are manufactured.
- the quaternary ammonium halides are generally prepared at 50-80% active concentrations.
- Alkali salts of dithiocarbamic acids are usually prepared at 20-50% active concentration. Dry forms of both reactants may also be used. The ratio of the reactants to water may also vary from about 10:90 to about 90:10, e.g. less than the amount of water present in the standard dithiocarbamate sodium salts.
- two phases are formed - a largely organic phase, containing the desired quaternary ammonium dithiocarbamate compound, and a largely aqueous phase containing the by-product salt.
- the aqueous phase may contain water-soluble impurities associated with one or both of the reactants. Upon standing, these phases separate into two distinct layers, and the organic-rich layer containing the desired product is recovered. The aqueous layer is discarded.
- phase separation can be assisted by the addition of extra salt to the aqueous phase and/or the addition of an organic solvent appropriate to the compound being made and compatible with its intended end use.
- the organic layer may be used as is, or diluted, or concentrated.
- novel compounds of the present invention may be made in situ where the reaction medium is an industrial water desired to be treated with biocide compositions of the invention.
- the reactants may be fed at concentrations as low as less than 5 ppm and the reaction occurs in situ to form the biocide compositions of the invention at ordinary levels of use. At such high dilution, phase separation does not occur, and solubility limits are never exceeded.
- the novel compounds in the organic layer after separation can also be carefully dried to a low water content.
- novel compounds of the present invention are particularly useful in fuels and other hydrocarbon solutions.
- the novel compounds of the invention may also be washed with water while in the organic-rich phase. The water separates rapidly out of this phase, leaving the novel compound with a particularly low chloride or sulfate content, which is desirable in a number of the uses for these compounds.
- a product of this invention may also be produced desirably in a form free from inorganic salts by using a calcium dithiocarbamate salt to react with a quaternary ammonium sulfate or methosulfate.
- An appropriate calcium dithiocarbamate salt is conveniently prepared by mixing under appropriate conditions of temperature and pressure 1 mole of, dimethylamine (or another selected amine), 1 mole of carbon disulfide, and 1/2 mole of calcium hydroxide ("slaked lime"). Generally lime is precharged to enough water to produce a final product concentration of about 25-35%. Alternately or simultaneously, the dimethylamine and carbon disulfide are then added from pressurized load cell feed tanks. When the pressure drops, the reaction is complete. The product has a pH of about 11-12 and the lime, which is originally present as a slurry, is all dissolved and reacted.
- the resulting calcium dithiocarbamate may be reacted according to the invention using either a quaternary ammonium sulfate or metho sulfate.
- the calcium sulfate formed by the reaction of the dithiocarbamate salt with a quaternary ammonium sulfate is essentially insoluble in water and can thus be removed by filtration of either the total reaction mixture or the organic-rich layer after removal of the water layer.
- All of the compounds of the present invention may be employed as surfactants for a variety of uses based on their surface active behavior at the appropriate dilutions.
- the surface active properties of compounds of the present invention also make them desirable as additives for de-emulsifiers for crude oils, thickeners for high water fluids, and in substances which aid in the flotation of heavy metal ores.
- the inorganic salts NaCl, KCl, Na 2 SO 4 , etc
- these products are characterized by a different solubility in water than that of their parent anion and cation.
- compositions for microbicidal use e.g., to control the growth of bacteria, fungi and yeasts.
- Compounds generally described by the foregoing formulas are effective against microorganisms, such as Pseudomonas sp I., Ps. aeruginosa, Staph. aureus, E. coli, and against fungi, such as Candida tropicalis, Penicillium, and Aspergillus niger.
- the compounds particularly effective against fungi are those in which R 1 and R 2 are methyl, R 3 and R 4 are C 6 -C 19 alkyl, and R 5 and R 6 are ethyl e.g. see Table I, example 18.
- These compounds may also be used for their anti-bacterial action as "in-can" preservatives to keep a product from degrading while in a container, e.g. paint.
- microbicidal compounds may also be used in cold sterilization of surgical and dental instruments in hospital sterilization processes.
- compounds of the instant invention When used as microbiocidal agents against bacteria or fungi, compounds of the instant invention may be applied directly to the surface to be protected or may be dissolved in a pharmaceutical carrier.
- an effective amount e.g. 0.1 to about 80% by weight of the compound, is included in an inert carrier and optionally a dispersing or surface active agent.
- an effective amount e.g. 0.1 to about 60% by weight, may be incorporated into a solid carrier which may be inert, such as talc, clay, diatomaceous earth, flour, and the like.
- the novel compounds of the invention having microbiocidal function are desirably used in industrial water treatment where the concentration thereof can be as low as 1-5 ppm.
- one or more of the novel compounds is present in any conventional formulation at an end use concentration which may vary within wide limits.
- the quantity of each novel dithiocarbamate compound should not be less than 1 ppm, nor for practical purposes exceed 100 ppm.
- the effective amount or concentration of the active ingredient used will vary according to the specific formulations and depending on its intended use.
- the novel compounds are desirably in higher concentrated form, e.g. 1% of compound. It is within the skill of the particular art for the end user to make dilutions appropriate to the desired end use. For example, household cleaners generally will have a much lower concentration of compounds in the end use product than would compositions for wood preservation.
- compositions may contain additional conventional components, such as suitable carriers, solvents, and surface active materials depending on the use to which the composition is directed. Additionally, the compositions may contain other conventional active ingredients or disinfecting agents in the desired formulation. Conventional solvents such as water ethanol, acetone, n-propyl alcohol, and/or isopropyl alcohol may be employed in the composition. Similarly, conventional surface active materials may be added to the composition. Optional additional known disinfecting ingredients such as formaldehyde, other known dithiocarbamate compounds or derivatives, or glyoxal may form part of the biocidal composition. These additional ingredients are added to the composition in a manner and to an extent familiar to those of skill in the art.
- compositions of the invention reside in their reduced toxicity to humans, high effectiveness against a wide variety of microorganisms, compatibility with known disinfectant reagents and chemical stability for purposes of storage.
- compositions of the present invention may also be employed in other areas, e.g. in water treatment, in oil drilling or recovery operations, in fuel, cutting fluids and others.
- Compounds of the present invention are also useful in hard surface cleaners. For this use, a high concentration of a biocidal compound of this invention of about 1% to about 20% is preferred.
- a formula for such a hard surface cleaning compound may be readily compounded by one of skill in the art using conventional ingredients in addition to a compound of the present invention.
- the compounds of the present invention also have a variety of uses in household products. For example, when added to water at high dilution these compounds can kill mildew and thus are applicable for use in cleansing products. Additionally, compounds of the present invention are compatible with non-ionic cleaning compounds additives over a wide range. For example, such products may contain from 5% nonionic surfactant with 95% of a compound of the present invention through the range of 95% of nonionic surfactant to 5% of a compound of the present invention. Such mixtures may be formulated to contain from 0.1% to about 20% biocidal compound, 10% to about 95% water, and the balance being surfactants and other inert materials.
- a presently preferred range for a use in cleansers is about 75% to 25% nonionic with about 25% to 75% of a compound of the present invention.
- the compounds may be used in non-cleaning household products such as fabric softeners because of their anti-static action.
- An additional use for compounds of the present invention are in preserving wood against infestation of insects, larvae, parasites and nematodes, algae and fungi.
- Compounds of the present invention would prevent wood rot. They would not leech out of the wood as do certain conventional wood preservatives, because the compounds of the present invention are soluble in oils and hydrocarbons.
- an effective wood preservative treatment would be to impregnate wood with a compound according to the present invention at 10 ppm per weight of wood.
- a desirable concentration range for such use is from .1% to 2% with a prefered concentration of .5%.
- the compounds are also useful for spraying onto wood chip piles to be used for making paper to prevent deterioration or incorporation into wax emulsion for coating wood.
- the application of a compound of the present invention to wood could be used in finished lumber for above ground use and in treating wood for use below ground.
- such compounds may be used in the paper industry for treating dilute pulp suspensions or white water to prevent the growth of "slime" at dilutions of up to 1 ppm.
- the concentrations of the products of this invention in the composition to be added to the paper machine may range from 1% to about 50%.
- compositions of the present invention are as additives to distillate and residual fuels. These compounds may prevent static generation in the fuel and simultaneously provide anti-microbial action at the water-fuel interface as well as corrosion inhibition. They are particularly adaptable for this use because they dissolve in hydrocarbon. These effects make them particularly interesting as additives to jet fuels.
- E.P. additives in lubricating oils.
- Such a composition containing a compound of the invention is particularly useful to reduce friction at the tool metal interface, in the cutting, machining and deforming of metals.
- compounds of the present invention would replace chlorinated paraffin and sulfur compounds which have been noted respectively to be carcinogenic or insufficiently active.
- Compounds of this invention may also be incorporated in synthetic, semisynthetic, or emulsion-type grinding, stamping, rolling and drawing fluids and in lubricating compounds containing no oil because of their water soluble and surfactant properties.
- the compounds may be added to semi-synthetic cutting or grinding fluids which contain a minor amount of oil. In cutting and grinding fluids the compounds are particularly desirable as additives because of their emulsifying ability and extreme pressure, lubricity and anti-microbial qualities. Additionally, these compounds do not cause skin irritation as do other E.P. additives.
- compositions containing pyridine quaternary ammonium dithiocarbamates are particularly interesting for corrosion inhibition purposes in the production and processing of oil.
- Compounds of the invention may also be used to control bacterial growth in water flooding in secondary oil recovery processes.
- the compounds for use in this process may inhibit the iron sulfide and dithiocarbamate formation and precipitation in the injection water.
- Such reduced reactivity with soluble iron makes this use valuble.
- compounds such as Table I, example 7 may be used for such a use at a concentration of 1-5 ppm.
- these compounds are additionally useful in the flotation of heavy metal ores in mineral beneficiation. Such compounds display selective absorption with certain ores and make the surface hydrophobic, allowing them to be separated by froth flotation.
- the following examples are provided for illustration only and are not intended to limit the scope of the invention in any way.
- Adogen 432 is a commercially available average di-C 15 alkyldimethyl ammonium chloride sold by Sherex Corp.
- Sunthene 410 is a 100 sec. deep refined naphthenic mineral oil sold by Sun Oil Company
- PB750 describes a benzyl quaternized polyalkyl pyridinium chloride sold by Lonza
- Volnopol NM is sodium dimethyldithiocarbamate sold by Alco Chemical
- Varisoft LT is dioleylamidoethyl dihydroxyethyl ammonium sulfate sold by Sherex.
- Varisoft 3690 is a 75% methyl-1-oleyl amidoethyl 2-oleyl imidazolinium methyl sulfate sold by Sherex Corp; 7) Igepal CO-630 is a nonylphenol with 9 E.O. sold by GAF; 8) Yarmol 302 is a pine oil sold commercially by Hercules Corp.; 9) BTC-851 is a 50% active alkyl (50% C 14 , 40% C 12 , 10% C 16 ) dimethylbenzyl ammonium chloride from Onyx Corp.; 10) Aliquat 336 PTC is 90% active tricaprylyl methyl ammonium chloride from Henkel Corp. Example 1. Novel quaternary ammonium dithiocarbamates.
- the remaining organic phase (187 g.) is alkyl (50% C 14 , 40% C 12 , 10% C 10 ) dimethylbenzyl ammonium diethyldithiocarbamate (85% active).
- the product has a slight haze which clears on standing.
- Table I below lists the R 1 - R 4 and R 7 , R 8 groups for several novel quaternary ammonium dithiocarbamates produced by this method.
- the compounds of Table I examples 5 and 6 were subjected to time-kill tests to determine effectiveness in terms of concentration of biocide (ppm) with time (hours).
- the target microorganism was Pseudomonas aeruginosa.
- Test tubes containing 10 ml of tryptic soy broth were dosed with the following levels of the compounds of Table I examples 5 and 6: 0, 50, 100, 200, 400, 600 and 1,000 ppm. Replicates were made of each dose so that quantitative measurements could be made at each time point (2, 4, , 8, 10 and 24 hours). After biocide addition, the tubes were inoculated with the microorganism. The bacterial count per ml at time zero was 2 ⁇ 10 6 /ml. Plate counts of all doses were made at each time point. The results for the compound of Example 5 are shown in the upper portion of Table III and for the compound of Example 6 in the lower portion of Table III.
- the compound of Table 1 example 6 was subjected to time-kill tests against Desulfovibrio desulfuricans (Mid-Continent Strain 4).
- a pure culture of the microorganism was grown in API RP 38 standard broth.
- Sufficient amounts of the biocide were added to 9.5 ml glass vials so that desired biocide concentrations were achieved when the vials were filled.
- the culture used to fill each vial measured about 10 6 colony forming units (cfu)/ml at time zero.
- Replicates of each level were made so that quantitative measurements of D. desulfuricans could be made at 2, 4, 6, 8, 10 and 24 hours. Parts per million levels of biocide were 5, 10, 15 and 20. Each level was done in duplicate.
- novel quaternary ammonium dithiocarbamate compounds of the present invention may be used in a variety of microbicidal or anti-bacterial compositions.
- An oil soluble emulsifier was prepared by mixing 246.0 grams (0.322 equivalents) Adogen 432, 69% active in water, with 225.0 grams (0.322 equivalents) of a 24.4% solution of sodium diethyldithiocarbamate in water and allowing the mixture to separate overnight. A lower layer of salt solution was separated and discarded leaving 262.3 grams of a solution of the product.
- a novel compound of the present invention, dialkyl (C 15 ) dimethyl ammonium diethyl dithiocarbamate formed an emulsifiable concentrate for, e.g. addition to cutting fluids, lubricants and for other corrosion inhibiting uses, after dilution in 10 to 40 parts water.
- the composition was prepared by mixing to form a clear solution: 74% by weight Sunthene 410, 13% by weight of a emulsifier containing tallow amine plus 2 moles ethylene oxide, and 13% by weight of the Adogen 432 salt of diethyldithiocarbamate (68% active).
- the sodium dimethyldithiocarbamate salt may be converted to a surface action agent (emulsifier) by converting it into the salt of
- R 1 is the alkyl of oleic acid.
- 1 mole (888 g.) of Sherex's Varisoft LT was mixed with good stirring with 1 mole, (358 g.) of a 40% solution of sodium dimethyldithiocarbamate [Alco Chemical].
- Tricaprylmethylammonium dimethyldithiocarbamate was 100% active and soluble at 1 to 99% in mineral spirits with no haze.
- decyloxypropyl bis 2-hydroxyethylmethyl ammonium dimethyldithiocarbamate is prepared by reacting 49.3 g. of 75% active decyloxypropyl bis-2-hydroxyethylmethyl ammonium chloride [Tomah Q-14-2] with 35.75 g. of 40% active sodium dimethyldithiocarbamate. The mixture was clear and had low viscosity. It was diluted stepwise and observed at each successive dilution. It remained clear down to 0.14% active product salt, but was hazy at 0.08% active. Thus this product is soluble at concentrations above its critical micelle concentration and insoluble below its CMC.
- Example 4 Novel Compounds for Corrosion Inhibition and Fuel Additives
- a variety of these compounds may also be used as additives to petroleum fuels to increase the efficiency thereof, provide anti-static action and aid in the inhibition of corrosion and rust.
- These compounds may be substituted for presently used compounds in so-called detergent fuels and other petroleum products.
- compounds according to this invention may also be employed in cooling towers to stabilize the chloride in the water and inhibit corrosion of the towers. Additionally, compounds according to this invention may be used as additives to cutting fluids to assist in the lubrication of the tool face; and in water flooding uses to avoid the formation of bacterial slime by Desulfovibrio desulfuricans and to inhibit the precipitation of iron and carbon.
- A For example, to prepare a highly water insoluble compound according to the invention, which has corrosion inhibition and metal deactivation properties, 55 grams of a solution of PB750 was stirred with 55 grams of a 40% solution of sodium dimethyldithiocarbamate, and allowed to separate to give 105 ml of inorganic rich layer.
- the alkyl pyridines are the by-products residues from the production of aldehyde collidine.
- the compound formed is extremely insoluble in water, much less than 10ppm.
- oil soluble quaternary ammonium dimethyldithiocarbamates may be prepared as follows:
- oil soluble quaternary ammonium dialkyl dithiocarbamate salts were prepared from tri-n-butyl methyl ammonium chloride, and tetra-n-butyl ammonium chloride.
- Example 5 Novel Compounds as Cleansers and Other Household Uses
- the compounds of the invention exhibit a compatible emulsification and synergy with the components of pine oil.
- a similar emulsion prepared from 30 pts d-limonene, 30 pts alkyl (50% C 14 , 40% C 12 , 10% C 16 ) dimethyl benzyl diethyl, dithiocarbamate (80% in water), 30 pts nonylphenol and 9 moles of ethylene oxide, 40 pts water, and 20 pts dipropylene glycol methyl ether forms a thin, essentially clear microemulsion readily dilutable into water, and is an effective hard surface cleaner with germicidal properties when diluted 1:64 in water.
- a formulation suitable as a rinse cycle softener was prepared from 5 parts of the Adogen 432 dimethyldithiocarbamate salt [Sherex] 1 to 5 parts of a nonionic surfactant and 90 to 94 parts water.
- Another example is the compound methyl 1-oleylamidoethyl 2-oleyl imidazolinium dimethyldithiocarbamate.
- Varisoft 3690 0.1 mole
- sodium dimethyldithiocarbamate 0.1 moles
- the cloudy mixture was intimately mixed and allowed to stand overnight.
- 35 g. of water containing the sodium methosulfate separated.
- the remaining product is 31% active. This product when solubilized with from 0.2 to 1 parts of a nonionic surfactant on the weight of the active product makes an effective rinse cycle softener and biocidal agent for home laundry applications.
- Example 1 The composition described in the preceding Example 1 was also shown to be a superior emulsifier for a pine oil cleaner formulation compared to the corresponding chloride salt normally used in such formulations.
- the formula: 8.05% Igepal CO-630, 7.95% Pine Oil (Yarmor 302), 8.00% isopropanol, 4.95% Antimicrobial (either Onyx BTC-851 or a novel compound of the invention) and 70.05% water were combined according to conventional methods.
- the emulsion using Onyx BTC-851 as the antimicrobial was unstable.
- Using the corresponding dimethyldithiocarbamate salt as the antimicrobial gave a transparent, stable micro-emulsion.
- the latter salt was prepared according to the method of Example 1 from 35% g. of Onyx's BTC-851 and 180 g.
- a composition suitable for use as a metal working fluid may be prepared using as a lubricating ingredient compounds of the present invention.
- a lubricating ingredient compounds of the present invention may consist of 0.1 to 10% of one or more of the compounds of claim 1, in which R 1 has at least 12 carbon atoms; 2 to 90% mineral oil, 5 to 50% of a supplemental emulsifier, such as petroleum sulfonates, rosin and tall oil soaps, and phosphate esters of nonionic surfactants, 0 to 20% ethoxylated fatty amines, and 0 to 80% water.
- This composition is suitable for dilution at 1:5 to 1:100 in water for application to a metal surface being cut, machine ground, or deformed.
- a concentrated fluid suitable for dilution at 1:5 to 1:100 for use as a lubricant for the cutting, grinding, machining, and drawing of metal may be prepared from the following: 0.1 to 10% one or more of the compounds of this invention having lubricating properties, 0 to 90% of a nonionic surfactant, 0 to 20% of an anionic surfactant, and 0 to 10% of an ethoxylated amine.
- the concentration of the two surfactants and the amine equals at least the concentration of the novel compound.
- This composition on dilution preferably has a pH of over 7.5 and is a clear solution.
- compositions and methods of the present invention may be obvious to those of skill in the art upon review of the teachings of this specification.
- the compounds of this invention may be included in a variety of formulations depending on the specific use desired. Additionally, these compounds may be sold at varying concentrations by a manufacturer, generally at high concentrations. The concentrations may be further diluted by intermediate sellers or end users. Such varied concentrations and formulations, the preparation of which is within the skill of the art, and other modifications are believed to be encompassed by the scope of the appended claims.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Dentistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Zoology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
On a mis au point des composés de dithiocarbamate d'ammonium quaternaire ayant la formule (I) ou (II), ainsi que des procédés permettant leur préparation consistant à mélanger dans de l'eau un composé d'ammonium quaternaire ayant la formule (III) et un sel de dithiocarbamate ayant la formule (i) ou un sel de bio-dithiocabamate tel que représenté par la formule (ii), et à récupérer le composé de dithiocarbamate d'ammonium quaternaire résultant de la couche organique ainsi formée. Les compositions employant de tels composés sont en premier lieu utiles comme tension-actifs et comme biocides.Quaternary ammonium dithiocarbamate compounds having the formula (I) or (II) have been developed, as well as methods for their preparation comprising mixing in water a quaternary ammonium compound having the formula (III) ) and a dithiocarbamate salt having the formula (i) or a bio-dithiocabamate salt as represented by the formula (ii), and recovering the quaternary ammonium dithiocarbamate compound resulting from the organic layer thus formed. The compositions employing such compounds are primarily useful as tension-active agents and as biocides.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18598288A | 1988-04-25 | 1988-04-25 | |
US185982 | 1988-04-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0368956A1 true EP0368956A1 (en) | 1990-05-23 |
EP0368956A4 EP0368956A4 (en) | 1990-09-26 |
Family
ID=22683176
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890905248 Withdrawn EP0368956A4 (en) | 1988-04-25 | 1989-04-13 | Quaternary ammonium dithiocarbamate compounds |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0368956A4 (en) |
AU (1) | AU3544289A (en) |
WO (1) | WO1989010956A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5130473A (en) * | 1986-05-15 | 1992-07-14 | Petrolite Corporation | Dithiocarbamate compounds |
US5371280A (en) * | 1990-11-09 | 1994-12-06 | Nippon Shokubai Co., Ltd. | Polymerization inhibitor and inhibiting method for vinyl compound |
US5247087A (en) * | 1992-05-13 | 1993-09-21 | Baker Hughes Incorporated | Epoxy modified water clarifiers |
US5380468A (en) * | 1992-10-20 | 1995-01-10 | Man-Gill Chemical Company | Aqueous alkaline composition for cleaning aluminum and tin surfaces |
WO1998005206A1 (en) * | 1996-08-02 | 1998-02-12 | Hickson International Plc | Quaternary ammonium salt compositions, and methods for treating substrates |
US6274199B1 (en) | 1999-01-19 | 2001-08-14 | Chemical Specialties, Inc. | Wood treatment process |
AP2014007573A0 (en) * | 2011-10-18 | 2014-04-30 | Cytec Tech Corp | Froth flotation processes |
US9574149B2 (en) * | 2011-11-11 | 2017-02-21 | Afton Chemical Corporation | Fuel additive for improved performance of direct fuel injected engines |
US10814306B2 (en) | 2015-07-27 | 2020-10-27 | 6th Wave Innovations Corp. | Molecularly imprinted polymer beads for extraction of metals and uses thereof |
WO2018085626A1 (en) * | 2016-11-03 | 2018-05-11 | 6th Wave Innovations Corp. | Molecularly imprinted polymer beads for extraction of lithium, mercury, and scandium |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354085A (en) * | 1965-05-28 | 1967-11-21 | Chevron Res | Lubricants containing quaternary ammonium dithiocarbamates |
DD245361A1 (en) * | 1986-01-24 | 1987-05-06 | Bitterfeld Chemie | Bactericides and fungicides |
-
1989
- 1989-04-13 EP EP19890905248 patent/EP0368956A4/en not_active Withdrawn
- 1989-04-13 AU AU35442/89A patent/AU3544289A/en not_active Abandoned
- 1989-04-13 WO PCT/US1989/001543 patent/WO1989010956A1/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354085A (en) * | 1965-05-28 | 1967-11-21 | Chevron Res | Lubricants containing quaternary ammonium dithiocarbamates |
DD245361A1 (en) * | 1986-01-24 | 1987-05-06 | Bitterfeld Chemie | Bactericides and fungicides |
Non-Patent Citations (1)
Title |
---|
See also references of WO8910956A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1989010956A1 (en) | 1989-11-16 |
AU3544289A (en) | 1989-11-29 |
EP0368956A4 (en) | 1990-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8592358B2 (en) | Storage-stable, synergistic microbicidal concentrates containing an isothiazolone, an amine and an oxidizing agent | |
US8765657B2 (en) | Antimicrobially effective use solutions comprising combinations of isothiazolones and amines | |
US4105431A (en) | 3-Isothiazolones as biocides | |
US5716628A (en) | Synergistic biocide composition containing pyrithione plus an additive | |
JP4361735B2 (en) | Preservative mixture containing quaternary ammonium compounds | |
JPH0699255B2 (en) | Novel microbial lethal mixture and method of treating water with it | |
AU2002255640A1 (en) | Preservative blends containing quaternary ammonium compounds | |
US3981998A (en) | Bactericidal and fungicidal 1,3,5 trialkanol triazines | |
EP0368956A1 (en) | Quaternary ammonium dithiocarbamate compounds | |
US5276047A (en) | Liquid 1,2-benzoisothiazoline-3-one preparation | |
JPS62230704A (en) | Liquid preparation of 1,2-benzisothiazoline-3-one, manufacture and use | |
CA2053678A1 (en) | Liquid 1,2-benzoisothiazoline-3-one preparation | |
KR100354981B1 (en) | Aqueous base fluid composition with improved antimicrobial properties | |
US3567420A (en) | Use of certain polyamines as antimicrobial agents | |
US5055493A (en) | Antimicrobial composition and method of use in oil well flooding | |
US20230392094A1 (en) | Metal working fluids biocide | |
KR19990008147A (en) | Use in bacteriostatic compositions and metalworking fluids | |
WO1998049898A1 (en) | Novel biocidal agents comprising quarternary bisimidazoline surfactants | |
US3733421A (en) | Microbiocidal nitrogen derivatives of halogenated biphenyls | |
US3790678A (en) | Microbiocidal nitrogen derivatives of halogenated biphenyls | |
GB1582774A (en) | Quaternary ammonium compounds the preparation and the use thereof | |
JPH02243604A (en) | Industrial anti-mold agent | |
JPH05117107A (en) | Industrial bactericide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19900224 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 19900607 |
|
R18W | Application withdrawn (corrected) |
Effective date: 19900607 |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 19900808 |
|
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |