WO1992004167A1 - Method of producing metal soap - Google Patents
Method of producing metal soap Download PDFInfo
- Publication number
- WO1992004167A1 WO1992004167A1 PCT/GB1991/001481 GB9101481W WO9204167A1 WO 1992004167 A1 WO1992004167 A1 WO 1992004167A1 GB 9101481 W GB9101481 W GB 9101481W WO 9204167 A1 WO9204167 A1 WO 9204167A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- metal soap
- soap
- fatty acid
- copper
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Definitions
- THIS invention relates to a method for producing metal soaps. More particularly it relates to a method for producing certain metal soaps which are suitable for use in preserving wood.
- a method of producing a metal soap comprises the steps of reacting a source material of one or more fatty acids with aqueous potassium hydroxide, reacting the resultant saponified fatty acid with a water soluble metal oxide or a metal salt of which the anion is selected from the group capable of forming a water soluble salt with potassium, allowing the reaction mixture to separate into an organic phase and an aqueous phase and recovering the metal soap from the organic phase.
- the phase separation may be enhanced by mixing the aqueous reaction products with a substantially water immiscible organic solvent, allowing phase separation to occur, and separating the organic and aqueous phases.
- the fatty acid source material may be a fatty acid or a mixture of fatty acids.
- the fatty acid is preferably linoleic acid.
- the source material may comprise a fat or vegetable oil.
- Sunflower fatty acid is a fraction of sunflower oil and is obtainable from Silicate and Chemical Industries, Durban.
- the metal of the metal soap to be produced is preferably at least one of zinc, copper, chromium, zirconium, iron, antimony, lead or mercury or any other known in the art as being suitable to be applied to wood. In the preferred form of the invention, however, the metal is copper or zinc.
- the metal salt for use in reacting the saponified fatty acid may be selected from the group comprising metal oxides, metal sulphates, metal chlorides and metal carbonates.
- metal oxides, metal sulphates, metal chlorides and metal carbonates it is preferred to use copper oxide, copper sulphate, copper chloride or copper carbonate.
- the reactions are preferably carried out at an elevated temperature which is maintained below the polymerisation temperature of the resultant metal soap.
- the reactions are preferably carried out at a temperature above about 40°C and below about 90°C.
- the separation of the resultant metal soap is prefer ⁇ ably carried out by mixing the aqueous reaction products with an organic solvent selecting from the group consisting of methylethylketone, methyl isobutyl ketone or diisobutyl ketone.
- the separated metal soap may be stripped from the methylethylketone by distillation under reduced pressure and the concentrate so obtained may thereafter be taken up into solution in a suitable carrier which may be selected from the group comprising xylene, toluene, low aromatic white spirits, high aromatic white spirits, monoethyleneglycol, monopropyleneglycol , a mixture of Shellflex DAR/Normal Butyl Alcohol [90:10 ratio by volume].
- a suitable carrier which may be selected from the group comprising xylene, toluene, low aromatic white spirits, high aromatic white spirits, monoethyleneglycol, monopropyleneglycol , a mixture of Shellflex DAR/Normal Butyl Alcohol [90:10 ratio by volume].
- the metal soap solution so obtained may be used as such as a wood preservative or diluted in a suitable solvent carrier for application in any convenient manner to timber to be treated.
- the solution may further be modified to render it water dispersible by formulation of an emulsifiable concentrate or microemulsion concentrate by using one or more appropriate surface active agents as is known in the trade.
- insecticides such as synthetic pyrethroids e.g. permethrin, cypermethrin, deltamethrin or alphamethrin may be incorporated into the formulation.
- the formulation may also incorporate a colouring agent, anti-foam agents, surfactants, anti-oxidants, moldicides, flame retardant compositions, and wood stabilizing agents.
- the soap may be produced as a neutral soap by ensuring stoichiometric equivalence between the metal and the fatty acid content, or as a basic soap by ensuring an abundance of copper ions or as an acid soap by ensuring an oversupply of fatty acids in the reaction mixture.
- reaction may be carried out in sequential steps but may also be carried out in a "one-pot" procedure.
- the Potassium Hydroxide pre-dissolved in water is added to the reaction vessel followed by the distilled sunflower fatty acid oil.
- To the resultant Potassium salt is added the pre-dissolved Copper Sulphate pentahydrate.
- the temperature is raised to between 85 and 90 degrees centigrade over a period of 45 minutes at a linear rate.
- the mixture is allowed to post-react for a period of 30 minutes between 85 and 90 degrees centigrade.
- Methyl Ethyl Ketone is added to the reactor contents and allowed to mix for 5 minutes. Mixing is discontinued and the mixture allowed to separate into three phases.
- the aqueous phase [bottom] containing dissolved salts [Potassium Sulphate], Methyl Ethyl Ketone [8-10% m] and traces of copper is transferred to a distillation vessel where the Methyl Ethyl Ketone is recovered.
- the middle emulsion phase is transferred and added to the recovered Methyl Ethyl Ketone ex the aqueous phase. This mixture is re-cycled in a subsequent batch prior to the Methyl Ethyl Ketone addition stage.
- the top phase constituting the copper fatty acid soap containing predominantly Copper Linoleate dissolved in Methyl Ethyl Ketone and 5-6% m water is filtered and then transferred to a distillation vessel where the Methyl Ethyl Ketone and Water is recovered for re ⁇ cycling.
- the resultant yield of copper fatty acid soap was 185 parts.
- To the copper fatty acid soap is added Xylene and the soap/Xylene mixture is transferred to a storage vessel for use at a minimum Cu content of 5% [m/m] .
- Methyl Ethyl Ketone and Methyl Ethyl Ketone/Emulsion phase are added at 70°C, i.e., when the soap is visually seen to be forming.
- Example 2 the basic procedure as described in Example 1 is modified in that the Distilled Fatty Acid and aqueous Copper Sulphate pentahydrate are added to the reaction vessel and heated to 40°C. At this point aqueous Potassium Hydroxide is added to the reactants at a linear rate over a period of 30 to 45 minutes. During the addition of Potassium Hydroxide the temperature is raised by the application of heat to between 85 and 90 C C. The reactor contents are allowed to post-react for a period of 15 minutes at this temperature. At this point mixing is stopped and the aqueous brine phase allowed to separate. The brine is then removed from the reaction vessel.
- the Distilled Fatty Acid and aqueous Copper Sulphate pentahydrate are added to the reaction vessel and heated to 40°C.
- aqueous Potassium Hydroxide is added to the reactants at a linear rate over a period of 30 to 45 minutes.
- the temperature is raised by the application of heat to between 85 and 90 C C.
- the reactor contents are allowed
- the reactor contents consisting of copper soaps [the continuous phase] and aqueous brine [the disperse phase] is subjected to agitation • for a period of 5 to 10 seconds. This enables the disperse phase to disassociate from the continuous phase and settle to the bottom of the reaction vessel upon discontinuation of the agitation. This second brine is then removed. Xylene is then added to the copper soaps and the product filtered and then transferred to a holding vessel.
- the aqueous Potassium Hydroxide is added to the reaction mixture at between 40 and 85°C, i.e. KOH addition is preferably commenced at about 85°C while taking care that the temperature does not exceed 90°C. Once the aqueous KOH addition is started, it is continued for between 30 to 45 minutes. Although heating is applied during the addition the temperature is not allowed to exceed the polymerization temperature of copper soaps.
- Methyl Ethyl Ketone is added to the reaction contents after the second brine removal to assist in the removal of small quantities of brine still dispersed in the copper soaps. Methyl Ethyl Ketone is then removed from the brine by distillation and added to the emulsion phase. This mixture is then re-cycled in a subsequent batch just prior to the Methyl Ethyl Ketone addition stage. The Methyl Ethyl Ketone in the copper soaps is removed by distillation and re-cycled.
- the copper soaps may be subjected to a reduced pressure distillation to remove any water trapped in the copper soaps, prior to the addition of the make-up solvent.
- any solvent which forms an azeotrope with water may be used in an atmospheric or reduced pressure distillation to remove any water trapped in the copper soaps, eg. Toluene and Xylene.
- an emulsion breaker may be added to the reaction mixture in amounts ranging from 50 to 250 ppm.
- emulsion breaker is Dissolvan V2243 ex Hoechst.
- Crude Sunflower Oil in which the fatty acids exist predominantly in the form of triglycerides may also be used as feedstock in Examples 1, 2 and 3.
- these feedstocks must first be saponified with an amount of Potassium Hydroxide [as an aqueous solution] equivalent to the saponi ication value of either the Crude Sunflower Oil depending on which is being used.
- the glycerol formed during this process is removed with a brine solution [Sodium Chloride in water].
- the Potassium salt is then processed into the Copper salt as per the procedures described in the Examples [excluding the saponification step] as per the following recipe :-
- the cut-back solvent used in all the procedures described above an be used to extract any Copper Linoleate dispersed in the brine phases described above and then added to the Copper Linoleate. This ensures maximum recovery of product and reduced effluent treatment.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
A method of producing a metal soap comprising the steps of reacting a source material of one or more fatty acids with aqueous potassium hydroxide, reacting the resultant saponified fatty acid with a water soluble metal oxide or a metal salt of which the anion is selected from the group capable of forming a water soluble salt with potassium, allowing the reaction mixture to separate into an organic phase and an aqueous phase and recovering the metal soap from the organic phase.
Description
METHOD OF PR UCING MSTAL SOAP
THIS invention relates to a method for producing metal soaps. More particularly it relates to a method for producing certain metal soaps which are suitable for use in preserving wood.
In our co-pending application entitled "WOOD PRESERVATIVES" which is incorporated herein by reference, we disclose the use of certain metal soaps, particularly mixtures of copper linoleate and other copper salts of fatty acids as wood preservatives. It is an object of the present invention to provide an improved method for producing such metal soaps.
It has been suggested in the literature to produce metallic soaps of fatty acids by neutralising the acid with caustic soda [NaOH] in water, and by the subsequent addition of a metal salt to the neutralised mixture to precipitate the metal salt. The precipitate is reported to be in the form of a slurry containing about 10% of the metallic soap and is then filtered and washed to recover the soap. [See "Fatty Acids, Their Chemistry, Properties, Production and Uses, 2nd Edition, Edited by K.S. Mar ley, Part 2 pp. 723, 714 and 749. ]
It has now been found that by performing the neutralisation with potassium hydroxide rather than NaOH it is possible to avoid a slurry precipitate to
recover high yields of the metallic soap in relatively pure form from a clearly separated phase in the reaction mixture.
According to the present invention a method of producing a metal soap comprises the steps of reacting a source material of one or more fatty acids with aqueous potassium hydroxide, reacting the resultant saponified fatty acid with a water soluble metal oxide or a metal salt of which the anion is selected from the group capable of forming a water soluble salt with potassium, allowing the reaction mixture to separate into an organic phase and an aqueous phase and recovering the metal soap from the organic phase. The phase separation may be enhanced by mixing the aqueous reaction products with a substantially water immiscible organic solvent, allowing phase separation to occur, and separating the organic and aqueous phases.
The fatty acid source material may be a fatty acid or a mixture of fatty acids. The fatty acid is preferably linoleic acid. Alternatively the source material may comprise a fat or vegetable oil.
In a specific form of the invention it relates to the method described above when used to produce a metal soap mixture from sunflower fatty acid as a starting material. Sunflower fatty acid is a fraction of
sunflower oil and is obtainable from Silicate and Chemical Industries, Durban.
The metal of the metal soap to be produced is preferably at least one of zinc, copper, chromium, zirconium, iron, antimony, lead or mercury or any other known in the art as being suitable to be applied to wood. In the preferred form of the invention, however, the metal is copper or zinc.
The metal salt for use in reacting the saponified fatty acid may be selected from the group comprising metal oxides, metal sulphates, metal chlorides and metal carbonates. Thus, in the production of copper linoleate or a copper linoleate rich metal soap it is preferred to use copper oxide, copper sulphate, copper chloride or copper carbonate.
The reactions are preferably carried out at an elevated temperature which is maintained below the polymerisation temperature of the resultant metal soap. Thus, the reactions are preferably carried out at a temperature above about 40°C and below about 90°C.
The separation of the resultant metal soap is prefer¬ ably carried out by mixing the aqueous reaction products with an organic solvent selecting from the group consisting of methylethylketone, methyl isobutyl
ketone or diisobutyl ketone.
The separated metal soap may be stripped from the methylethylketone by distillation under reduced pressure and the concentrate so obtained may thereafter be taken up into solution in a suitable carrier which may be selected from the group comprising xylene, toluene, low aromatic white spirits, high aromatic white spirits, monoethyleneglycol, monopropyleneglycol , a mixture of Shellflex DAR/Normal Butyl Alcohol [90:10 ratio by volume].
The metal soap solution so obtained may be used as such as a wood preservative or diluted in a suitable solvent carrier for application in any convenient manner to timber to be treated. The solution may further be modified to render it water dispersible by formulation of an emulsifiable concentrate or microemulsion concentrate by using one or more appropriate surface active agents as is known in the trade.
Further, alternatively, other insecticides such as synthetic pyrethroids e.g. permethrin, cypermethrin, deltamethrin or alphamethrin may be incorporated into the formulation.
The formulation may also incorporate a colouring agent, anti-foam agents, surfactants, anti-oxidants,
moldicides, flame retardant compositions, and wood stabilizing agents.
It will be appreciated that the soap may be produced as a neutral soap by ensuring stoichiometric equivalence between the metal and the fatty acid content, or as a basic soap by ensuring an abundance of copper ions or as an acid soap by ensuring an oversupply of fatty acids in the reaction mixture.
The reaction may be carried out in sequential steps but may also be carried out in a "one-pot" procedure.
The invention will now be illustrated with reference to the production of copper linoleate. It will be understood, however, that the invention is not limited to this product.
EXAMPLE 1
MANUFACTURING PROCESS FOR COPPER FATTY ACID SOAPS
[CuLin]
Ingredients Quantity by Mass
Distilled Sunflower Fatty Acid 169 parts
Potassium Hydroxide 39 parts
Water 221 parts
Copper Sulphate Pentahydrate 74 parts
Water 497 parts
Methyl Ethyl Ketone 500 parts
Xylene 190 parts
The Potassium Hydroxide pre-dissolved in water is added to the reaction vessel followed by the distilled sunflower fatty acid oil. To the resultant Potassium salt is added the pre-dissolved Copper Sulphate pentahydrate. The temperature is raised to between 85 and 90 degrees centigrade over a period of 45 minutes at a linear rate. The mixture is allowed to post-react for a period of 30 minutes between 85 and 90 degrees centigrade. At this stage Methyl Ethyl Ketone is added to the reactor contents and allowed to mix for 5 minutes. Mixing is discontinued and the mixture allowed to separate into three phases. The aqueous phase [bottom] containing dissolved salts [Potassium Sulphate], Methyl Ethyl Ketone [8-10% m] and traces of copper is transferred to a distillation vessel where the Methyl Ethyl Ketone is recovered. The middle emulsion phase is transferred and added to the recovered Methyl Ethyl Ketone ex the aqueous phase. This mixture is re-cycled in a subsequent batch prior to the Methyl Ethyl Ketone addition stage. The top phase constituting the copper fatty acid soap containing predominantly Copper Linoleate dissolved in Methyl Ethyl Ketone and 5-6% m water is filtered and
then transferred to a distillation vessel where the Methyl Ethyl Ketone and Water is recovered for re¬ cycling. The resultant yield of copper fatty acid soap was 185 parts. To the copper fatty acid soap is added Xylene and the soap/Xylene mixture is transferred to a storage vessel for use at a minimum Cu content of 5% [m/m] .
During the distillation and reaction stages of the process the temperature is not allowed to exceed 90°C. This is done to prevent polymerisation of Copper Linoleate and other fatty acid soaps.
EXAMPLE 2
In a variation to the procedure of Example 1, the Methyl Ethyl Ketone and Methyl Ethyl Ketone/Emulsion phase are added at 70°C, i.e., when the soap is visually seen to be forming.
EXAMPLE 3
In this procedure which follows the basic steps of Example 1, the Methyl Ethyl Ketone addition is omitted and separation of the aqueous or brine phase is done in two stages. The first separation occurs when mixing is stopped and the brine allowed to settle. This so- called first brine is then removed. The reactor
contents consisting of Copper Linoleate and other fatty acid soaps as the continuous phase and brine as the disperse phase is subjected to agitation for approximately 5 to 10 seconds. This enables the disperse phase to disassociate from the continuous phase and settle to the bottom of the reaction vessel. This so-called second brine is then removed from the vessel. To the reactor contents which consist of copper fatty acid soaps and a small quantity of brine dispersed in the copper fatty acid acid soap is added Xylene. This mixture is agitated and filtered before being transferred to a holding vessel.
EXAMPLE 4
In this procedure the basic procedure as described in Example 1 is modified in that the Distilled Fatty Acid and aqueous Copper Sulphate pentahydrate are added to the reaction vessel and heated to 40°C. At this point aqueous Potassium Hydroxide is added to the reactants at a linear rate over a period of 30 to 45 minutes. During the addition of Potassium Hydroxide the temperature is raised by the application of heat to between 85 and 90CC. The reactor contents are allowed to post-react for a period of 15 minutes at this temperature. At this point mixing is stopped and the aqueous brine phase allowed to separate. The brine is then removed from the reaction vessel. The reactor
contents consisting of copper soaps [the continuous phase] and aqueous brine [the disperse phase] is subjected to agitation • for a period of 5 to 10 seconds. This enables the disperse phase to disassociate from the continuous phase and settle to the bottom of the reaction vessel upon discontinuation of the agitation. This second brine is then removed. Xylene is then added to the copper soaps and the product filtered and then transferred to a holding vessel.
EXAMPLE 5
In a variation of the procedure of Example 4, the aqueous Potassium Hydroxide is added to the reaction mixture at between 40 and 85°C, i.e. KOH addition is preferably commenced at about 85°C while taking care that the temperature does not exceed 90°C. Once the aqueous KOH addition is started, it is continued for between 30 to 45 minutes. Although heating is applied during the addition the temperature is not allowed to exceed the polymerization temperature of copper soaps.
EXAMPLE 6
In a further variation of the procedure of Example 4, Methyl Ethyl Ketone is added to the reaction contents after the second brine removal to assist in the removal
of small quantities of brine still dispersed in the copper soaps. Methyl Ethyl Ketone is then removed from the brine by distillation and added to the emulsion phase. This mixture is then re-cycled in a subsequent batch just prior to the Methyl Ethyl Ketone addition stage. The Methyl Ethyl Ketone in the copper soaps is removed by distillation and re-cycled.
BYAlfPLE 7
In Examples 4, 5 and 6 the copper soaps may be subjected to a reduced pressure distillation to remove any water trapped in the copper soaps, prior to the addition of the make-up solvent.
Alternatively, any solvent which forms an azeotrope with water may be used in an atmospheric or reduced pressure distillation to remove any water trapped in the copper soaps, eg. Toluene and Xylene.
EXAMPLE 8
To further improve phase separations in any of the Example 1 through to 7 an emulsion breaker may be added to the reaction mixture in amounts ranging from 50 to 250 ppm. .An example of such an emulsion breaker is Dissolvan V2243 ex Hoechst.
Crude Sunflower Oil in which the fatty acids exist predominantly in the form of triglycerides may also be used as feedstock in Examples 1, 2 and 3. However, these feedstocks must first be saponified with an amount of Potassium Hydroxide [as an aqueous solution] equivalent to the saponi ication value of either the Crude Sunflower Oil depending on which is being used. The glycerol formed during this process is removed with a brine solution [Sodium Chloride in water]. The Potassium salt is then processed into the Copper salt as per the procedures described in the Examples [excluding the saponification step] as per the following recipe :-
Ingredient Quantity
Potassium salt 240."1 parts
Copper Sulphate pentahydrate 98.5 parts
Water 661.4 parts
The cut-back solvent used in all the procedures described above an be used to extract any Copper Linoleate dispersed in the brine phases described above and then added to the Copper Linoleate. This ensures maximum recovery of product and reduced effluent treatment.
Many variations in detail may be thought of without
thereby departing from the spirit .of the invention,
Claims
1. A method of producing a metal soap comprising the steps of reacting a source material of one or more fatty acids with aqueous potassium hydroxide, reacting the resultant saponified fatty acid with a water soluble metal oxide or a metal salt of which the anion is selected from the group capable of forming a water soluble salt with potassium, allowing the reaction mixture to separate into an organic phase and an aqueous phase and recovering the metal soap from the organic phase.
2. The method of claim 1 wherein the aqueous reaction mixture is mixed with a substantially immiscible organic solvent.
3. The method of claim 1 wherein the source material is linoleic acid.
4. The moethod of claim 1 wherein the source material is sunflower fatty acid.
5. The method of claim 1 wherein the metal of the metal soap to be produced is selected from the group consisting of zinc, copper, chromium, zirconium, iron, antimony, lead, mercury.
6. The method of claim 1 wherein the metal salt for use in reacting the saponified fatty acid is selected from the group consisting of metal sulphates, metal chlorides and metal carbonates.
7. The method of claim 1 characterised in that the reactions are carried out at an elevated tempera¬ ture which is maintained below the polymerisation temperature of the resultant metal soap and preferably at a temperature above about 40°C and below about 90°C.
8. The method of claim 1 wherein the separation of the metal soap is carried out by mixing the aqueous reaction products with an organic solvent selecting from the group consisting of methyl- ethylketone, methyl isobutyl ketone or diisobutyl ketone and wherein the separated metal soap is optionally stripped from the ketone by distillation under reduced pressure and the con¬ centrate so obtained is taken up into solution in a suitable carrier which is selected from the group comprising xylene, toluene, low aromatic white spirits, high aromatic white spirits, mono- ethyleneglycol, monopropyleneglycol, a mixture of Shellflex DAR/Normal Butyl Alcohol [90:10 ratio by volume] .
9. A wood preservative composition containing a metal soap produced by the method of any one of claims 1 to 8.
10. The wood preservative composition of claim 9 optionally containing at least one of another insecticide such as synthetic pyrethroids e.g. permethrin-, cypermethrin, deltamethrin or alphamethrin, a colouring agent, anti-foam agents, surfactants, anti-oxidants, moldicides, flame retardant compositions, and wood stabilizing agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA907004 | 1990-09-03 | ||
| ZA90/7004 | 1990-09-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992004167A1 true WO1992004167A1 (en) | 1992-03-19 |
Family
ID=25580284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1991/001481 Ceased WO1992004167A1 (en) | 1990-09-03 | 1991-09-02 | Method of producing metal soap |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU8521991A (en) |
| NZ (1) | NZ239635A (en) |
| WO (1) | WO1992004167A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4220161A1 (en) * | 1992-06-19 | 1993-12-23 | Stefes Pflanzenschutz Gmbh | New formulations of active ingredients for plant protection and method of use |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3262889A (en) * | 1962-02-27 | 1966-07-26 | M & T Chemicals Inc | Liquid anhydrous stannous soap compositions |
| US4158648A (en) * | 1971-12-12 | 1979-06-19 | Canadian Patents And Development Limited | Pressure- and heat-sensitive coatings |
| EP0005361A2 (en) * | 1978-05-05 | 1979-11-14 | Cuprinol Limited | Anti-fungal compositions and method of preserving materials therewith |
| DD220321A1 (en) * | 1983-11-21 | 1985-03-27 | Petrolchemisches Kombinat | PAINT CARE, CLEANSING AND PRESERVATIVE |
| GB2168394A (en) * | 1984-12-18 | 1986-06-18 | Mooney Chemicals | Aqueous water-repellent and fungicidal systems |
| JPS638347A (en) * | 1986-06-27 | 1988-01-14 | Nippon Oil & Fats Co Ltd | Production of higher alcohol |
| US4783221A (en) * | 1986-12-12 | 1988-11-08 | Mooney Chemicals, Inc. | Compositions and process for preserving wood |
| JPH02178250A (en) * | 1988-12-28 | 1990-07-11 | Nippon Oil & Fats Co Ltd | Production of metallic soap |
-
1991
- 1991-09-02 NZ NZ239635A patent/NZ239635A/en unknown
- 1991-09-02 WO PCT/GB1991/001481 patent/WO1992004167A1/en not_active Ceased
- 1991-09-02 AU AU85219/91A patent/AU8521991A/en not_active Abandoned
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3262889A (en) * | 1962-02-27 | 1966-07-26 | M & T Chemicals Inc | Liquid anhydrous stannous soap compositions |
| US4158648A (en) * | 1971-12-12 | 1979-06-19 | Canadian Patents And Development Limited | Pressure- and heat-sensitive coatings |
| EP0005361A2 (en) * | 1978-05-05 | 1979-11-14 | Cuprinol Limited | Anti-fungal compositions and method of preserving materials therewith |
| DD220321A1 (en) * | 1983-11-21 | 1985-03-27 | Petrolchemisches Kombinat | PAINT CARE, CLEANSING AND PRESERVATIVE |
| GB2168394A (en) * | 1984-12-18 | 1986-06-18 | Mooney Chemicals | Aqueous water-repellent and fungicidal systems |
| JPS638347A (en) * | 1986-06-27 | 1988-01-14 | Nippon Oil & Fats Co Ltd | Production of higher alcohol |
| US4783221A (en) * | 1986-12-12 | 1988-11-08 | Mooney Chemicals, Inc. | Compositions and process for preserving wood |
| JPH02178250A (en) * | 1988-12-28 | 1990-07-11 | Nippon Oil & Fats Co Ltd | Production of metallic soap |
Non-Patent Citations (4)
| Title |
|---|
| C.R.HEBD. SEANCES ACAD. SCI., SER. C vol. 263, no. 18, 2 November 1966, PARIS E. ANDRE ET J. HENRY: 'Etude comparée de la force saponifiante des solutions aqueuses de potasse, de soude et de lithine.' * |
| WORLD PATENTS INDEX LATEST Week 8530, 17 February 1985 Derwent Publications Ltd., London, GB; AN 85-177895 & DD,A,220 321 see abstract * |
| WORLD PATENTS INDEX LATEST Week 8808, 14 January 1988 Derwent Publications Ltd., London, GB; AN 88-052813 & JP,A,63 008 347 (NIPPON OILS) see abstract * |
| WORLD PATENTS INDEX LATEST Week 9034, 11 July 1990 Derwent Publications Ltd., London, GB; AN 90-256430 & JP,A,2 178 250 (NIPPON OILS) see abstract * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4220161A1 (en) * | 1992-06-19 | 1993-12-23 | Stefes Pflanzenschutz Gmbh | New formulations of active ingredients for plant protection and method of use |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8521991A (en) | 1992-03-30 |
| NZ239635A (en) | 1993-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US1947989A (en) | Method of oxidizing hydrocarbons | |
| EP0182118B1 (en) | Highly concentrated pumpable aqueous pastes of alkaline salts of alkyl esters of alpha-sulphonated fatty acids, and process for their preparation | |
| US3804819A (en) | Recovery of fatty acids from tall oil heads | |
| US2206168A (en) | Process for manufacturing fatty esters | |
| DE4019781A1 (en) | METHOD FOR PRODUCING MONOETHYLENICALLY UNSATURATED CARBONIC ACID ESTERS | |
| EP0186895A2 (en) | Process for the epoxidation of olefinic unsaturated hyrocarbons with peracetic acid | |
| EP1644469A1 (en) | Process for preparing purified fatty acids | |
| US2463015A (en) | Method of treating animal and vegetable oils | |
| US4483791A (en) | Recovery of fatty acids from tall oil heads | |
| US2525702A (en) | Purification of oil | |
| WO1992004167A1 (en) | Method of producing metal soap | |
| DE1219484B (en) | Process for the production of peroxycarboxylic acids | |
| CA1206975A (en) | Process for refining triglyceride oils | |
| US4730067A (en) | Process for the preparation of zirconium carboxylate | |
| US1943427A (en) | Production of organic acids | |
| CA2466911A1 (en) | Method for commercial preparation of conjugated linoleic acid using spent alkali transesterification catalyst | |
| DE69819208T2 (en) | METHYLESTER-BASED METHOD FOR THE PRODUCTION OF MONOGLYCERIDE | |
| US3872142A (en) | Method of purifying alkali metal soaps of synthetic fatty acids | |
| US2721221A (en) | Propanol extraction of sodium vanillinate | |
| EP0524996B1 (en) | Process for manufacturing light-coloured washing alpha-sulpho-fatty-acid low-alkyl ester salts | |
| JPS6045228B2 (en) | How to make natural colorants | |
| US4064117A (en) | Recovery of fatty acids from tall oil heads | |
| ZA200601185B (en) | Process for preparing purified fatty acids | |
| US2499877A (en) | Extraction of unsaponifiables from wool grease | |
| US2369108A (en) | Selective oxidation of unsaturated fatty bodies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AT AU BB BG BR CA CH DE DK ES FI GB HU JP KP KR LK LU MC MG MW NL NO PL RO SD SE SU US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU ML MR NL SE SN TD TG |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: CA |