WO1997023281A1 - Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants - Google Patents
Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants Download PDFInfo
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- WO1997023281A1 WO1997023281A1 PCT/IB1996/001408 IB9601408W WO9723281A1 WO 1997023281 A1 WO1997023281 A1 WO 1997023281A1 IB 9601408 W IB9601408 W IB 9601408W WO 9723281 A1 WO9723281 A1 WO 9723281A1
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- surfactant
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- fatty acid
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- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
Definitions
- the present invention relates to organosilicone/surfactant blends that are characterized by improved clarity, wetting and spreading properties.
- Nonionic surfactants are commonly used in agriculture as adjuvants to improve the efficacy of pesticides, micronutnents, biologicals, herbicides, fungicides, growth regulators and the like. Surfactants are important in the application, wetting, spreading and emulsifying either as pan of the formulation or as part of a tank mix.
- Nonionic surfactants are well known lor their ability to reduce the surface tension of aqueous solutions. This reduction in surface tension is important for the spreading of solutions on difficult to wet surfaces such as the waxy surface of plant leaves Surtactants aid in uptake. Though conventional nonionic surfactants aid in wetting of spray formulations. they do not proude total wetting on hydrophobic leaf surfaces
- Organosilicone compounds have been found to be significantly useful as agricultural adjuvants because of their unique wetting properties. These surfactants give surface tension value significantly lower than conventional nonionic surfactants and can provide significant uptake of agricultural chemicals into the plant
- organosilicone compound must be insoluble in water and dispersed in order to spread extensively . i.e.. superspread. Organosilicone compounds that were soluble in water did not superspread. (Superspreading of WaterSilicone Surfactant on Hydrophobic Surfaces. S . Zhu et al., Colloids Surfaces. a-Physicochem. Eng. Aspects 90 (1994). 63-78) The interaction between surfactant pairs, while documented, is not consistent. Some pairs demonstrate an ideal behavior where the pair provides the results that would be expected from the mixture whereas some pairs are non-ideal in providing surface tensions lower than that expected.
- U.S. Pat No. 3.562.786 describes solutions of nonionic organosilicone compounds blended with certain ranges of conventional nonionic and ionic surfactants.
- the organosilicone compound is claimed to be useful in lowering the aqueous surface tension of organic surfactant solutions.
- the nonionic surfactants used in the patented combinations are primarily nonylphenol or alcohol ethoxylates. However, these materials when used with organosilicone compounds are known to interfere with the spreading characteristics of the organosilicone compounds.
- U.S. Pat. No 5.104.647 teaches the synergistic combination of organosilicone compounds with polyalkylene oxide block copolymers which forms dispersions allowing for good surface tension reduction without sacrificing the spreading efficacy of the mixture.
- Nonylphenol or alcohol ethoxylates interfere with the spreading characteristics of the organosilicone compounds since they do not form dispersions.
- the 5.104.647 patent teaches that the weight fraction of organosilicone compound to poK alkylene oxide block copolymer can range from 1 % to 99% and conversely the copolymer from 99% to 1%.
- the preferred ranges are from 1 % to 50% and 50% to 1 % These later ranges correspond with the ranges taught in the 3.562.786 patent where the weight ratio between the organosilicone compound and the surfactant ranges from 0.001 to 1 to 1/1. In both these instances, the prior art is taught to use less organosilicone compound than surfactant in order to obtain the desired results. No superspreading or lowering of the contact angle was taught.
- the surfactant mixture of this invention provides an improved dynamic and equilibrium surface tension values when compared to the individual components of the mixture.
- the present invention provides an improved surfactant blend characterized by improved superspreading which comprises an organosilicone compound as defined herein mixed with specific water-soluble surfactant(s).
- This surfactant blend provides clear aqueous solutions with low surface tension without sacrificing the spreading efficacy of the mixture.
- the surfactant blend is especially useful in agricultural applications as an adjuvant for the delivery of agriculturally active ingredients such as fertilizers, micronutrients. biologicals, and pesticides such as herbicides, fungicides insecticides and growth regulators, to treatment sites.
- Figure 1 is a graphic representation of the data of Example 1 illustrating the degree of non-ideal behavior observed with a mixture of BOS and SILWET L-77.
- Figure 2 is a graphic representation of the data of Example 1 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L-77 and BOS.
- Figure 3 is a graphic representation of the data of Example 2 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L-77 and MPOB Na sulfate.
- Figure 4 is a graphic representation of the data of Example 2 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L-77 and MBOP Na phosphate.
- Figure 5 is a graphic representation of the data of Example 3 illustrating the degree of non-ideal behavior observed with mixtures of SILWET L-77 and DA-530.
- Figure 6 is a graphic representation of the data of Example 4 illustrating the synergism in dynamic surface tension verses bubble surface age for SILW ⁇ T L-77. DSB and their mixtures.
- organosilicone compound(s) which can be used in the present invention can be represented by the general formula:
- M represents Me 3 SiO 1.2 (represents Me 3 SiO or Me 3 Si as necessary to form a chemically complete structure);
- D represents Me 2 SiO:
- D' represents MeRSiO: Me equals CH 3 ;
- R equals C n H 2n O(C 2 H 4 O) a (C 3 H 6 O) b
- y ranges from about 0 to 5. preferably zero;
- x ranges from about 1 to 5.
- n ranges from about 2 to 4.
- oxyalkylene groups may be random and/or block mixtures: and R' can be hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl ester group wherein the alkyl group of the ester has 1 to 4 carbon atoms.
- R' can be same or different on any given molecule.
- R' is hydrogen or a methyl group.
- organosilicone compounds can be represented by the following examples:
- the most preferred organosilicone compound is represented by the following formula:
- organosilicone compounds useful in the invention can be prepared by several conventional methods such as by a process that involves forming a mixture of a siioxane polymer containing a silicon-bonded, halogen-substituted monovalent hydrocarbon group and an alkali metal salt of an oxyalkylene polymer and heating the mixture to a temperature sufficiently elevated to cause the siioxane polymer and the salt to react to produce the desired compound. Some of these compounds can be made by hydrosilation of allyl compounds.
- the water-soluble surtactants or surface acm e agents which provide the useful and unexpected benefits of the compositions of the invention are generally characterized structurally as having an elongated non-polar hydrophobic portion comprising from about a C 4 to about C 12 aliphatic moiety and a short polar hydrophilic portion.
- These surfactants can be classified as synthetic, sihcone-free, short chain, anionic, non-ionic and/or amphoteric.
- anionic surfactants include sulfates. phosphates, sulfonates. carboxylates and taurates In the anionic class, the most commercially important anion groups are carboxy (-COOH), sulfonic acid (-SO 3 H ) and sulfuric ester (-OSO 3 H)
- the anionic surfactants used herein include alkyl and alkyl ether sulfates and sulfonates. alkylaryl and alkylaryl ether sulfates and sulfonates. alcohol ether sulfates, ether carboxylic acids and salts thereof, ⁇ -olefin suifonate salts, alkyl (mono or di) sulfosuccinates. monoalkyl ether sulfosuccmates. alkyl sarcosinates. alkyl monoglyceride sulfate and sulfonates. acyl isethionates. acyl methyl taurates.
- salts of fatty acid and fatty acid esters and alkyl. alkylaryl. ethoxylate mono or di phosphate esters salts, fatty alcohol ether phosphate ester salts, condensates of fatty acids and amino acids, and mixtures thereof.
- surfactants can be used in admixture.
- alkyl is intended to mean an aliphatic straight, branched or cyclic C 4 -C 12 carbon chain such as butyl, capnl, caporyl, capryryl, alkylaryl is intended to mean alkyl as defined before and aryl is intended to cover benzene, naphthalene, such as nonylphenyl and dibutylnaphthyl and substituted derivatn es thereof such as nonylphenol.
- diphenyl oxide alcohol is intended to be coextensive with the definition for alkyl
- olefin is intended to cover an unsaturated carbon chain of 4 to 12 carbons
- acyl and fatty acid are intended to have a carbon chain of from 4 to 12 carbons
- ether or ethoxylate is intended to cover EO and/or PO of from 1 to 5. preferably from 1 to 4.
- the surfactant can also have a countenon which can be alkali metal of sodium or potassium, ammonium or mono, di or tri-ethanol amine.
- surfactants can be illustrated by ammonium or sodium 2-ethylhexyl sulfate or suifonate, sodium octyl sulfate, ammonium nonylphenyl ether sulfate (2 EO) disodium N-octyl sulfosuccinate: dibutyl naphthalene sodium suifonate, sodium mono or di - dodecyl diphenyl oxide disulfonate, sodium decyl naphthalene suifonate sodium octyl N-methyl taurates. disodium dioctyl sulfosuccinate.
- Non-ionic surfactants do not dissociate in water but nevertheless are characterized by a relatively polar portion and a relativeh non-polar portion.
- the nomonic surtactants used herein include fatty acid glycenne esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyglycerine fatty acid esters wherein the fatty acid has from 4 to 10 carbon atoms., higher alcohol ethylene oxide adducts. single long chain polyoxyethylene alkyl ethers, alkyl and alkylaryl ethoxylates.
- polyoxyethylene alkyl allyl ethers polyoxyethylene fatty acid esters, polyoxyethylene glycenne fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and polyoxyethylene fatty acid amides wherein the fatty acid has from 4 to 10 carbon atoms, polyoxyethylene alkyl amines, an alkylpyrrohdone, glucamides, alkylpolyglucosides, mono- and dialkanol amides, a poh oxyethylene alcohol mono- or diamides and alkylamine oxides wherein the aliphatic group ranges from 4 to 10 carbon atoms.
- Amphoteric surfactants form zwitterions in water so that the same molecule can act as either an anionic or a cationic surfactant.
- the amphoteric surfactants used herein include amino acid, betaine. sultaine. phosphobetaines. imidazoline type amphoteric surfactants.
- Amphoteric surfactants useful in the invention can be illustrated by disodium caporylo or capryio or capryrylo beta-aminodipropionate. C 4 -C 8 N-alkyI betaaminopropionic acid and the sodium salt thereof .
- amphocarboxylate is meant to include RC(O)NHCH 2 CH 2 N(R 1 )CH 2 CH 2 OH where R represents a fatty alkyl group of 4 to 10 carbons, and R 1 is an alkylcarboxy group of 2 to 3 carbon atoms in the alkyl group.
- gemini surfactants which is a term used herein to identify surfactants having two or three hydrophobic groups with a linkage between hydrocarbon chains and two or more hydrophilic groups attached to hydrophobic portions in the molecule.
- the hydrophilic and hydrophobic groups can be the same on either side of the linkage or different.
- a Gemini surfactant can be anionic. non-ionic, or amphoteric.
- gemini surfactants includes compounds of the formula:
- R independently represents alkyl of from about 4 to about 20 carbon atoms.
- R 1 independently represents hydrogen and alkyl of from about 4 to 20 carbon atoms:
- R 2 independently represents hydrogen. -SO 3 M, -OP(O)(OM) 2 , -CH 2 COOM, CH 2 CHOHCH 2 SO 3 M.
- M is hydrogen, alkali metal such as sodium, potassium. alkaline earth metal such as magnesium and calcium, ammonium or organic base salt: and
- R 3 represents alkylene of from one to about 10 carbon preferably from about 1 to about 4 atoms or -C(O)-R 4 -C(O)- wherein R 4 represents alkylene of from 1 to about 10 carbon atoms and aryl. e.g. phenylene.
- R 3 also represents -0-R 5 -O- wherein R 5 represents aliphatic or aromatic moieties of from 1 to about 10 carbon atoms with the proviso that when R 3 is alkylene, then R 2 is not hydrogen EO represents ethyleneoxy radicals.
- PO represents propyleneoxy radicals, a and b are numbers of from 0 to about 100. a is preferably from about 0 to about 30 and b is preferably from about 0 to 10 When R 2 is hydrogen, b is not zero and when R 2 is other than hydrogen, b is preferably zero Preferably .
- R 3 is alkylene and more preferably CH 2 .
- water-soluble gemini surfactants useful in the compositions of the present invention include disodium methylene bis-(octyl phenol sulfate). disodium methylene bis-(octyl phosphate), disodium methylene bis-(octyl phenol ethoxy ether sulfate). disodium methylene bis-(octyl phenol ethoxy ether phosphate).
- alkyl or “alkylene” include straight as well as branched chains.
- mixtures of the desired organic surfactants can also be used in compositions of the present invention in order to achieve desired performance.
- compositions of the invention can also include other surfactants, or additives normal to the industry including active components used as biocides. pesticides and the like with the qualification that the amount of these additional components is insufficient to totally negate the superspreading or other surfactant enhancing characteristics of the compositions of the invention.
- auxiliary additives may be suitably chosen for a desired composition and generally include inorganic salts such as Glauber salt and common salt, builders, humectants. solubilizing agents. UV absorbers, softeners, chelating agents. and viscosity modifiers.
- the organosilicone compound in the blend of organosilicone compound and the desired surfactants of the invention is used in amounts ranging from about 70% to about 95%. preferabh from about 80% to about 95%. and more preferably from about 85% to about 95% by weight based on the actives weight.
- the other surfactants of the invention are used in amounts ranging from about 30% to about 5%. preferably from about 20% to 5% and more preferably from about 15% to about 5% by weight actives.
- the mixtures of organosilicone and conventional surfactants as disclosed in the invention provide low surface tension and good dynamic surface tension properties. allowing coating formulations to rapidly attain low equilibrium surface tensions.
- the compositions of the invention can be used in treating a surface which rests the spreading of an aqueous treatment solution by applying to the surface in amount effective to improve the spreading of the treatment solution.
- These mixtures are effective wetting, spreading, leveling and flow control agents for vanous coating applications, especially in water-based systems, particularh for water-based coating processes designed for difficult to coat, low surface energy substrates.
- the surfactant blends of the present invention find particular utility as superspreading additives for paints and coatings, adhesives and adhesive controlled release agents, hard surface cleaners and particularly as adjuvants for dispersing, wetting and spreading agnculturally active ingredient-containing solutions such as micronutrients. fertihzers. biologicals. and pesticides such as herbicides, fungicides, insecticides, growth regulators, and the like and mixtures thereof.
- foliage or fruit applications from aqueous solutions have been found to be the most effective means for application. Success of foliage sprays depends on a number of factors, particularly the nature of the solution and the type of leaf or fruit surfaces involved.
- Plant surfaces are uneven, being ridged or composed of hemispherical cell walls. Water droplets assume spherical shapes with minimum contact surfaces. If the plant pan is in a vertical position or if the spray droplet has considerable momentum as it strikes the plant, an aqueous spray solution may bounce or run off to a large extent.
- aqueous sprays are repelled by most plant surfaces: they round up into spherical droplets and tend to run off. Even when atomized by high pressure and applied with great force, they do not stick to the waxy surfaces of many plants If they do stick, they stay in place or collect into droplets and present a minimum surface of contact.
- the surfactant blends of the present invention can improve the spreading characienstics of the spray solution, enhance dynamic and equilibnum surface tension values and assist in dispersing the pesticides.
- EXAMPLE 1 This example demonstrates that a surfactant blend of the compound of Formula II (SILWET L-77) and sodium 2-ethyIhexy l sulfate (RHODAPON BOS) displays strong nonideal solution behavior.
- the blends for the Examples were prepared by simple admixture.
- the performance of the surfactant mixtures set forth in this invention was evaluated by several methods. Surfactant interactions were determined bv equilibnum surface tension measurements by the Wilhelrm Plate Method using a Krüss K-12 Tensiometer at 25°C and dynamic surface tension measurements by the Maximum Bubble Pressure Method ( MBPM) using a kruss BP-2 Dynamic Surface Tensiometer at constant room temperature (22°C).
- the degree of interaction tor the surfactant mixtures is expressed as the difference between the expected and the observed values for surface tension.
- Synergy is defined as a reduction m surface tension below that of either individual surfactant.
- Non-ideal mixing is defined as a reduction in surface tension below that expected value for a linear relationship between two surfactant components.
- a smooth Parafilm surface was prepared by a) dipping a clean glass slide into a hot Parafilm solution in cyclohexane; b) evaporating the solvent in an oven at 60°C for one hour, c) cooling the slide covered by Parafilm down to room temperature (22°C) for 30 minutes before using 8 ⁇ l (0 008 gram) of a surfactant solution was applied to the smooth Parafilm surface.
- the spread area was recorded at 60 seconds.
- the spread ratio was calculated by dividing the spread area of 8 ⁇ l of distilled water into the spread area obtained using the same volume of surfactant solution.
- the surfactant solutions were freshh prepared before each evaluation using deionized water.
- FIG. 1 illustrates the degree of non-ideal behavior observed with a mixture of BOS and SILW ⁇ T L-77 Although the expected interaction profile for these non-ionic-anionic mixture is linear, the observed behavior is non-ideal in nature Similar interactions are observed with other anionic surfactants such as sodium octyl sulfate (RHODAPON OLS) and 2-ethylhexanol phosphate (RHODAFAC PEH).
- RHODAPON OLS sodium octyl sulfate
- RHODAFAC PEH 2-ethylhexanol phosphate
- Figure 2 shows the synergism in reduction of dynamic surface tension.
- the mixtures of L-77/BOS showed lower dynamic surface tension values than that of either individual component. This indicates that the L-77/BOS complexes diffuse from the aqueous solution to the air/water interface much faster than either L-77 or BOS individually.
- the faster spreading property of the mixture may be partially attributed to the synergism in the reduction in dynamic surface tension.
- a mixture of SILW ⁇ T L-77 and a non-ionic surfactant branched chain isodecyl alcohol ethoxylate with 4 EO groups also showed good spreading property and non-ideal behavior in surface tension reduction.
- Figure 5 illustrates the degree of non-ideal behavior observed with mixtures of DA-530 and SILW ⁇ T L-77. Although the expected interaction profile for these non-ionic surfactants is linear, the observed behavior is non-ideal in nature. Data on contact angle and spreading ratio of these mixtures on the Parafilm surface are listed in Table 6.
- MIRANOL JEM Conc. Mixtures of SILWET L-77 and C8-amphocarboxylate (MIRANOL JEM Conc.) demonstrated non-ideal behavior in surface tension reduction and synergistic interaction in dynamic surface tension reduction. Data on surface tension and spreading ratio on Parafilm surface are listed in Table 9.
Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96940063A EP0868211A1 (en) | 1995-12-21 | 1996-12-10 | Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants |
AU77058/96A AU709352B2 (en) | 1995-12-21 | 1996-12-10 | Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants |
BR9612271-4A BR9612271A (en) | 1995-12-21 | 1996-12-10 | Surfactant mixture of organosilicone and surfactants useful as an agricultural adjuvant |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US57674995A | 1995-12-21 | 1995-12-21 | |
US08/576,749 | 1995-12-21 |
Publications (1)
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WO1997023281A1 true WO1997023281A1 (en) | 1997-07-03 |
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PCT/IB1996/001408 WO1997023281A1 (en) | 1995-12-21 | 1996-12-10 | Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants |
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EP (1) | EP0868211A1 (en) |
AU (1) | AU709352B2 (en) |
BR (1) | BR9612271A (en) |
WO (1) | WO1997023281A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003595A1 (en) * | 1998-07-16 | 2000-01-27 | Michigan State University | Compositions and methods for protecting cultivated plants from herbicidal injury |
EP1064844A1 (en) * | 1999-06-30 | 2001-01-03 | Dow Corning Corporation | Surfactant blends containing organosilicone surfactants and diphenyl oxide sulfonate surfactants useful as agricultural adjuvants |
US6197876B1 (en) | 1999-02-24 | 2001-03-06 | Ck Witco Corporation | Heterocyclic amine modified siloxanes |
US6235681B1 (en) | 1998-12-10 | 2001-05-22 | Ck Witco Corporation | Terminally modified, amino, polyether siloxanes |
US7008904B2 (en) | 2000-09-13 | 2006-03-07 | Monsanto Technology, Llc | Herbicidal compositions containing glyphosate and bipyridilium |
US7507775B2 (en) | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
US7601680B2 (en) | 2005-12-13 | 2009-10-13 | Momentive Performance Materials | Gemini silicone surfactant compositions and associated methods |
US7645720B2 (en) | 2005-12-13 | 2010-01-12 | Momentive Performance Materials Inc. | Extreme environment surfactant compositions comprising hydrolysis resistant organomodified disiloxane surfactants |
US10745778B2 (en) | 2015-12-07 | 2020-08-18 | Basf Se | Leaching aids and methods of using leaching aids |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0332598A2 (en) * | 1988-03-08 | 1989-09-13 | Union Carbide Corporation | Silicone surfactants containing cyclic siloxane pendants |
US5104647A (en) * | 1990-06-22 | 1992-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Surfactant blend of organosilicone and polyalkylene oxide polymers useful as an agricultural adjuvant |
US5558806A (en) * | 1992-07-23 | 1996-09-24 | Osi Specialties, Inc. | Surfactant blend of a polyalkleneoxide polysiloxane and an organic compound having a short chain hydrophobic moiety |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0642304B1 (en) * | 1993-03-30 | 1998-09-09 | OSi Specialties, Inc. | Super-spreading, low-foam surfactant for agricultural spray mixtures |
-
1996
- 1996-12-10 EP EP96940063A patent/EP0868211A1/en not_active Withdrawn
- 1996-12-10 WO PCT/IB1996/001408 patent/WO1997023281A1/en not_active Application Discontinuation
- 1996-12-10 AU AU77058/96A patent/AU709352B2/en not_active Ceased
- 1996-12-10 BR BR9612271-4A patent/BR9612271A/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0332598A2 (en) * | 1988-03-08 | 1989-09-13 | Union Carbide Corporation | Silicone surfactants containing cyclic siloxane pendants |
US5104647A (en) * | 1990-06-22 | 1992-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Surfactant blend of organosilicone and polyalkylene oxide polymers useful as an agricultural adjuvant |
US5558806A (en) * | 1992-07-23 | 1996-09-24 | Osi Specialties, Inc. | Surfactant blend of a polyalkleneoxide polysiloxane and an organic compound having a short chain hydrophobic moiety |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003595A1 (en) * | 1998-07-16 | 2000-01-27 | Michigan State University | Compositions and methods for protecting cultivated plants from herbicidal injury |
US6235682B1 (en) * | 1998-07-16 | 2001-05-22 | Board Of Trustees Operating Michigan State University | Compositions and methods for protecting cultivated plants from herbicidal injury |
US6235681B1 (en) | 1998-12-10 | 2001-05-22 | Ck Witco Corporation | Terminally modified, amino, polyether siloxanes |
US6238684B1 (en) | 1998-12-10 | 2001-05-29 | Osi Specialties, Inc. | Terminally modified, amino, polyether siloxanes |
US6197876B1 (en) | 1999-02-24 | 2001-03-06 | Ck Witco Corporation | Heterocyclic amine modified siloxanes |
EP1064844A1 (en) * | 1999-06-30 | 2001-01-03 | Dow Corning Corporation | Surfactant blends containing organosilicone surfactants and diphenyl oxide sulfonate surfactants useful as agricultural adjuvants |
US7008904B2 (en) | 2000-09-13 | 2006-03-07 | Monsanto Technology, Llc | Herbicidal compositions containing glyphosate and bipyridilium |
US7989392B2 (en) * | 2000-09-13 | 2011-08-02 | Monsanto Technology, Llc | Herbicidal compositions containing glyphosate bipyridilium |
US7507775B2 (en) | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
US7601680B2 (en) | 2005-12-13 | 2009-10-13 | Momentive Performance Materials | Gemini silicone surfactant compositions and associated methods |
US7645720B2 (en) | 2005-12-13 | 2010-01-12 | Momentive Performance Materials Inc. | Extreme environment surfactant compositions comprising hydrolysis resistant organomodified disiloxane surfactants |
US8183317B2 (en) | 2005-12-13 | 2012-05-22 | Momentive Performance Materials Inc. | Coating compositions comprising hydrolysis resistant organomodified disiloxane surfactants |
US10745778B2 (en) | 2015-12-07 | 2020-08-18 | Basf Se | Leaching aids and methods of using leaching aids |
Also Published As
Publication number | Publication date |
---|---|
AU7705896A (en) | 1997-07-17 |
BR9612271A (en) | 2001-01-02 |
EP0868211A1 (en) | 1998-10-07 |
AU709352B2 (en) | 1999-08-26 |
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