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US3954967A Expired / Lapsed US ⏱️ 0.0 years remaining

Method of producing microcolloidal aqueous emulsions of unsaturated organic insecticidal compounds

Assignee: Vanguard Chemical Co Ltd
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Filing: 1974-04-10
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Granted: 1976-05-04
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Expires: 1994-04-10
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Abstract

Abstract A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound utilizes an ionic pumping action to achieve micelle division. The resin utilized is selected on the basis of the presence in the molecular chain of a high number of sites which can accept a positive ion to cause the molecule to assume an overall charge. A gross emulsion is first formed utilizing a sufficient quantity of surfactant so that an excess is present to assure surfacating of the newly formed micelles upon division of the micelles of the initial emulsion. The resin is equilibrated utilizing a compound capable of donating positive ions to the resin molecule to cause the molecule to assume a charge of the same sign as the sign of the charge on the emulsion micelles. The resulting increased charge in the emulsion results in division of the micelles into micelles of a smaller size. The resin pumping action can be continued until the micelles of the emulsion are characterized by an inability to reflect light of a visible wavelength.

Inventors

  • 👤 John T. Urton

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 06:45
CPC Classifications
A; A01; A01N; A01N25/00; A01N25/02; A01N25/04

Claims Analysis

Total Claims: 20
Claim 1
Independent Claim 362 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties, said compound being characterized by solubility in an organic polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing the internal phase of said emulsion by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to said emulsion a quantity of a water soluble resinous compound to comprise at least approximately 0.005% by weight of the subsequently formed microemulsion characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound, there being at least one site in each repeating monomer of the molecule; equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelle while maintaining a substantially constant pH in said emulsion; whereby the increased charge in the emulsion from the molecules of the resinous compound results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 2
Independent Claim 362 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties, said compound being characterized by solubility in an organic polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing the internal phase of said emulsion by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to said emulsion a quantity of a water soluble resinous compound to comprise at least approximately 0.005% by weight of the subsequently formed microemulsion characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound, there being at least one site in each repeating monomer of the molecule; equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelle while maintaining a substantially constant pH in said emulsion; whereby the increased charge in the emulsion from the molecules of the resinous compound results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 3
Dependent Claim 29 words
The method as set forth in claim 1, wherein said step of incorporating a chelating agent comprises utilizing dimethyl sulfoxide as the polar solvent for preparing said internal phase.
Claim 4
Dependent Claim 26 words
The method as set forth in claim 1, wherein said step of incorporating a chelating agent comprises adding to the emulsion a quantity of ethylenediaminetetraacetic acid.
Claim 5
Independent Claim 450 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing the internal phase of said emulsion by dissolving a quantity of said compound in an organic polar solvent, adding a quantity of surfactant to the resulting solution, and mixing of the surfactant and the solution, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; adding to said internal phase a quantity of a water soluble resinous compound selected from the group consisting of polyacrylic acid and pyrrolidone polymers in a quantity of at least 0.005% by weight of the subsequently formed microemulsion; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to said emulsion a second quantity, comprising at least 0.005% by weight of the subsequently formed microemulsion, of said resinous compound; and equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating a positive ion to the acid radical of said polyacrylic acid or to the amide radical of said pyrrolidone to cause the radical to assume a charge of the same sign as the sign of the charge on the emulsion micelles, said equlibrating step comprising equilibrating said resinous compound with a compound selected from the group consisting of sodium hydroxide, ammonium hydroxide, triethanolamine, monoethanolamine, and diisopropanolamine when said resinous compound is a polyacrylic acid polymer, and wherein said equilibrating step comprises equilibrating said resinous compound with hydrochloric acid when said resinous compound is a pyrrolidone polymer, said equilibrating step including the step of maintaining a substantially constant pH in the emulsion, whereby the increased charge in the emulsion from the molecules of said resinous compound results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 6
Independent Claim 450 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing the internal phase of said emulsion by dissolving a quantity of said compound in an organic polar solvent, adding a quantity of surfactant to the resulting solution, and mixing of the surfactant and the solution, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; adding to said internal phase a quantity of a water soluble resinous compound selected from the group consisting of polyacrylic acid and pyrrolidone polymers in a quantity of at least 0.005% by weight of the subsequently formed microemulsion; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to said emulsion a second quantity, comprising at least 0.005% by weight of the subsequently formed microemulsion, of said resinous compound; and equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating a positive ion to the acid radical of said polyacrylic acid or to the amide radical of said pyrrolidone to cause the radical to assume a charge of the same sign as the sign of the charge on the emulsion micelles, said equlibrating step comprising equilibrating said resinous compound with a compound selected from the group consisting of sodium hydroxide, ammonium hydroxide, triethanolamine, monoethanolamine, and diisopropanolamine when said resinous compound is a polyacrylic acid polymer, and wherein said equilibrating step comprises equilibrating said resinous compound with hydrochloric acid when said resinous compound is a pyrrolidone polymer, said equilibrating step including the step of maintaining a substantially constant pH in the emulsion, whereby the increased charge in the emulsion from the molecules of said resinous compound results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 7
Independent Claim 346 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: dissolving a quantity of said compound in a polar solvent; said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%; adding to the resulting solution a surfactant capable of forming a microemulsion which is soluble in the solution, in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; mixing said surfactant and the solution to form an internal phase; adding to said emulsion a second quantity, comprising at least 0.005% by weight of the subsequently formed microemulsion, of a water soluble resinous compound characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound; equilibrating said resinous compounds with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelles, while maintaining a substantially constant pH in the emulsion, whereby the increased charge in the emulsion from the molecules of the resinous compounds results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; continuing said equilibrating step until the resulting micelles of a smaller size are characterized by an inability to reflect light of a visible wavelength; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 8
Independent Claim 346 words
A method of reducing the micelle size of an aqueous emulsion of an unsaturated organic compound having insecticidal properties said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: dissolving a quantity of said compound in a polar solvent; said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%; adding to the resulting solution a surfactant capable of forming a microemulsion which is soluble in the solution, in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; mixing said surfactant and the solution to form an internal phase; adding to said emulsion a second quantity, comprising at least 0.005% by weight of the subsequently formed microemulsion, of a water soluble resinous compound characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound; equilibrating said resinous compounds with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelles, while maintaining a substantially constant pH in the emulsion, whereby the increased charge in the emulsion from the molecules of the resinous compounds results in division of the emulsion micelles into micelles of a smaller size to form a microemulsion; continuing said equilibrating step until the resulting micelles of a smaller size are characterized by an inability to reflect light of a visible wavelength; and incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to thereby increase the penetrability of said organic compound through said insect.
Claim 9
Dependent Claim 96 words
The method as set forth in claim 5, wherein said organic compound comprises pyrethrin, said dissolving step comprises dissolving a quantity of said pyrethrin in methyl alcohol; and including the additional step of adding a quantity of betahydroxytoluene to the solution, said step of adding a first quantity of a resinous compound comprising adding a quantity of a polyacrylic acid polymer to said internal phase, said step of incorporating a chelating agent comprising adding a quantity of ethylenediaminetetraacetic acid to the emulsion, and said equilibrating step comprising adding a quantity of sodium hydroxide to the emulsion.
Claim 10
Dependent Claim 114 words
The method as set forth in claim 5, wherein said organic compound comprises l-naphthyl N-methyl carbamate, said dissolving step comprises dissolving a quantity of said l-naphthyl N-methyl carbamate in a solution of approximately 40% by volume dimethyl sulfoxide and approximately 60% by volume methyl alcohol, said step of adding a surfactant comprising adding a quantity of polyoxyethylene sorbitan monostearate, said step of adding a first quantity of a resinous compound comprising adding a quantity of a polyacrylic acid polymer to said internal phase, said step of incorporating a chelating agent comprising adding a quantity of ethylenediaminetetraacetic acid to the emulsion, and said equilibrating step comprising adding a quantity of sodium hydroxide to the emulsion.
Claim 11
Dependent Claim 34 words
The method as set forth in claim 7, wherein there is included the step of adjusting the pH of said polyacrylic acid to approximately 6.8 before the same is added to said internal phase.
Claim 12
Independent Claim 363 words
A method of killing insects comprising the steps of: preparing the internal phase of an aqueous emulsion of an unsaturated organic insecticidal compound, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to the emulsion a quantity of a water soluble resinous compound to comprise at least approximately 0.005% by weight of the subsequently formed microemulsion characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound, there being at least one site in each repeating monomer of the molecule; incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to increase the penetrability of said insecticidal compound through said insect; equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelles without substantial change in the pH of the emulison, to increase the charge in the emulsion from the molecules of the resinous compound and thereby effect division of the emulsion micelles into micelles of a smaller size; and applying the equilibrated emulsion to an area where an insect will come into contact therewith.
Claim 13
Independent Claim 363 words
A method of killing insects comprising the steps of: preparing the internal phase of an aqueous emulsion of an unsaturated organic insecticidal compound, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous, by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; adding to the emulsion a quantity of a water soluble resinous compound to comprise at least approximately 0.005% by weight of the subsequently formed microemulsion characterized by the presence of a high number of positive ion accepting sites in each molecule of the resinous compound, there being at least one site in each repeating monomer of the molecule; incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to increase the penetrability of said insecticidal compound through said insect; equilibrating said resinous compound with a stoichiometric quantity of a compound capable of donating positive ions to said sites to cause the latter to assume a charge of the same sign as the sign of the charge on the emulsion micelles without substantial change in the pH of the emulison, to increase the charge in the emulsion from the molecules of the resinous compound and thereby effect division of the emulsion micelles into micelles of a smaller size; and applying the equilibrated emulsion to an area where an insect will come into contact therewith.
Claim 14
Independent Claim 226 words
A method of killing insects comprising the steps of: preparing the internal phase of an aqueous emulsion of an unsaturated organic insecticidal compound, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to increase the penetrability of said insecticidal compound through said instect; and applying said emulsion to an area where an insect will come into contact therewith.
Claim 15
Independent Claim 226 words
A method of killing insects comprising the steps of: preparing the internal phase of an aqueous emulsion of an unsaturated organic insecticidal compound, said compound being characterized by solubility in a polar solvent, and an absence of the elements iron, copper, zinc and phosphorous by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; diluting said internal phase to at least approximately 70% by volume water to form said emulsion; incorporating in the emulsion a chelating agent for the calcium ions present in the basil membrane of an insect to increase the penetrability of said insecticidal compound through said instect; and applying said emulsion to an area where an insect will come into contact therewith.
Claim 16
Independent Claim 244 words
A method of increasing the efficacy of an insecticidal compound, wherein said compound is an unsaturated organic compound characterized by solubility in an organic polar solvent and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing an aqueous solution of a water soluble polyacrylic acid polymer; partially equilibrating said polymer with a less than stoichiometric quantity of a base capable of reacting with the carboxyl groups of the polymer to yield water and a substituted polymer molecule; further equilibrating said polymer with a less than stoichiometric quantity of an amine selected from the group consisting of triamylamine, triethylamine, and di-(2-ethylhexyl)amine; preparing a solution of said compound by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; and combining said solutions to form an aqueous emulsion.
Claim 17
Independent Claim 244 words
A method of increasing the efficacy of an insecticidal compound, wherein said compound is an unsaturated organic compound characterized by solubility in an organic polar solvent and an absence of the elements iron, copper, zinc and phosphorous, said method comprising the steps of: preparing an aqueous solution of a water soluble polyacrylic acid polymer; partially equilibrating said polymer with a less than stoichiometric quantity of a base capable of reacting with the carboxyl groups of the polymer to yield water and a substituted polymer molecule; further equilibrating said polymer with a less than stoichiometric quantity of an amine selected from the group consisting of triamylamine, triethylamine, and di-(2-ethylhexyl)amine; preparing a solution of said compound by adding a quantity of said compound along with a quantity of surfactant to an organic polar solvent, said compound being present in a quantity such that the volume of the compound relative to the volume of the subsequently formed emulsion is no more than approximately 4%, and said solvent being present in a quantity such that the volume of the solvent relative to the volume of the subsequently formed emulsion is from 10% to 25%, said surfactant being characterized by the ability to form a microemulsion which is soluble in said polar solvent and said surfactant being present in a quantity of at least approximately two parts by volume of said surfactant to one part by volume of said compound; and combining said solutions to form an aqueous emulsion.
Claim 18
Dependent Claim 38 words
The method as set forth in claim 11, including the steps of: adding a saline solution to said emulsion to precipitate a complex comprising said compound and the substituted polymer; and removing said precipitate from the supernatant liquid.
Claim 19
Dependent Claim 21 words
The method as set forth in claim 12, wherein there is included the step of drying said precipitate to powder form.
Claim 20
Dependent Claim 33 words
The method as set forth in claim 12, wherein the step of preparing the aqueous solution comprises preparing said solution in a concentration of from 0.1 to 0.3% by weight of said polymer.

References Cited (Backward Citations)

US2134158A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1979-05-04 1979-11-03 1980-05-04 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1983-05-04 1983-11-03 1984-05-04 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1987-05-04 1987-11-03 1988-05-04 $7700.00 Window Closed / Lapsed

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