WO2000005950A1 - Latex polymeres prepares a partir de sels amines ethyleniquement insatures - Google Patents

Latex polymeres prepares a partir de sels amines ethyleniquement insatures Download PDF

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Publication number
WO2000005950A1
WO2000005950A1 PCT/US1999/017029 US9917029W WO0005950A1 WO 2000005950 A1 WO2000005950 A1 WO 2000005950A1 US 9917029 W US9917029 W US 9917029W WO 0005950 A1 WO0005950 A1 WO 0005950A1
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WIPO (PCT)
Prior art keywords
acids
surface active
latex
acid
amine
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Application number
PCT/US1999/017029
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English (en)
Inventor
Alfred K. Schultz
Adnan Siddiqui
Brett Butler
Original Assignee
Stepan Company
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Filing date
Publication date
Application filed by Stepan Company filed Critical Stepan Company
Priority to EP99935970A priority Critical patent/EP1100325A1/fr
Priority to BR9912572-2A priority patent/BR9912572A/pt
Priority to AU51333/99A priority patent/AU5133399A/en
Priority to CA002338708A priority patent/CA2338708A1/fr
Publication of WO2000005950A1 publication Critical patent/WO2000005950A1/fr

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    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • the present invention relates to an improved agricultural formulations derived from polymer latexes prepared by emulsion polymerization processes which utilize ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. More specifically, the invention relates to latex-based agricultural formulations produced from emulsion polymerization processes which utilize ethylenically unsaturated amine salts of alkylbenzene sulfonic acids, alkyl olefin sulfonic acids, alkyl alcohol sulfuric acid esters, or alkoxylated alkyl alcohol sulfuric acid esters, fatty acids, and fatty phosphate acid esters, or mixtures thereof, to form polymers, discrete solid polymeric particles and latexes.
  • the agricultural formulations of the present invention typically comprise a stable mixture of a polymer latex and a pesticide, herbicide, fungicide, or insecticide.
  • a method for using novel polymer latexes as delivery systems for pesticides is provided, wherein such systems show excellent stability, dispersion and dilution properties.
  • emulsion polymerization of ethylenically unsaturated monomers to form discrete solid polymeric particles for use in coating, sealant, adhesive and/or elastomer (CASE) applications is well known to the art.
  • These polymeric latexes have found wide spread use in the preparation of a variety of agricultural formulations, including herbicidal, pesticidal/insecticial, and fungicidal formulations.
  • Conventional emulsion polymerization of ethylenically unsaturated monomers employs one or more water soluble surfactants to emulsify the monomers and the resulting polymer products, i.e., latexes.
  • the monomers used in emulsion polymerization reactions are generally water-insoluble, but in some cases may be water-soluble.
  • a surfactant is used to suspend small portions of monomer in a continuous or semi-continuous aqueous phase.
  • the monomer molecules are suspended as small spheres in the aqueous phase, wherein the polymerization takes place within the small spheres.
  • the water soluble surface active agents, i.e., surfactants typically utilized in emulsion polymerization reactions are anionic, nonionic, and cationic surfactants or a mixture thereof.
  • the polymeric particles formed by the emulsion polymerization process are typically utilized in coating, sealant, adhesive and/or elastomer (CASE) applications and agricultural applications and formulations.
  • CASE elastomer
  • the surfactant does not become chemically bonded to the polymeric particles by carbon-carbon bond formation but rather remains in the polymeric particle product solution after the emulsion polymerization reaction is complete, i.e., all of the monomer(s) is reacted.
  • the unreacted surfactant can have a detrimental effect on the polymer product solution, as it can interfere with the performance of such polymerization products in CASE applications and agricultural formulations; the suspension of polymeric particles and/or agricultural technical may become destabilized over time and undergo unwanted coagulation and/or phase separation.
  • Non-polymerizable surfactant solutions to the traditional problems encountered in performing an emulsion polymerization process are numerous.
  • U.S. Pat. No. 3,941,857 describes the use of epoxy resins which react with the residual anionic, cationic or nonionic surfactant.
  • Polymerizable compounds such as allyl alcohol (and esters thereof) have been found to be ineffective due to the formation of undesirable high levels of coagulum in the final emulsion polymerization product. Additionally, see U.S. Pat. No. 4,224,455.
  • U.S. Pat. No. 3,156,661 describing water insoluble pesticides lindane and dieldrin incorporated into floor wax formulations using styrene and acrylic resinous materials; the final compositions are water-based and form coatings of flooring materials.
  • U.S. Pat. No. 4,303,642 discloses stable latexes comprising polymers containing chlo ⁇ yrifos or chlo ⁇ yrifos-methyl insecticide, which are prepared by mixing the latex with the insecticide.
  • U.S. Pat. No. 4,304,769 describes a process of blending a loadable polymeric latex into a solution of a hydrophobic material (i.e.
  • U.S. Pat. No. 4,336,173 involves a pre-emulsification, with a homogenizer, of a water insoluble substance with emulsifier, then combining the emulsion with a seed latex and a water soluble solvent.
  • EP 0 381 691 Bl discloses a method of reducing or eliminating incompatibility between two pesticidal active ingredients, by inco ⁇ orating one pesticide in a dispersed latex phase and the other ingredient within the continuous aqueous phase.
  • 5,188,824 discloses stable aqueous emulsion formulations of water-insoluble organic pesticides which are formed from a mixture of organic pesticide, structured particle latex and optionally a cosolvent and/or a cosurfactant.
  • U.S. Pat. No. 5,260,259 discloses a controlled release and delivery system for a hydrophobic, water sensitive herbicide, produced by mixing a pesticide dissolved in water-immiscible solvent, with a latex dispersion until the latex particles absorb the herbicide.
  • 5,321,049 discloses a water dilutable pesticidal composition, prepared by combining a pesticidal substance dissolved in a water-immiscible solvent, with an emulsifier and polymer latex to form a dispersion in water.
  • WO 96/02136 discloses a method of controlling the particle size and distribution of an aqueous emulsion using dispersions of templating agents and surfactants; polymer latexes are used as examples of template agents for controlling particle size of the emulsions.
  • herbicidal compositions are generally supplied in the form of wettable powders, emulsifiable concentrates and the like.
  • emulsifiable concentrates it is generally necessary to inco ⁇ orate substantial quantities of organic solvents, and this can result in substantial problems of dermal toxicity and flammability.
  • organic solvents because of the presence of organic solvents, it is not possible, for many emulsifiable concentrate compositions, to utilize containers of conventional plastics materials, such as high density polyethylene (HDPE). Instead, such concentrates have to be contained within specially designed containers, which are resistant to the solvents used.
  • HDPE high density polyethylene
  • the present invention utilizes a novel group of compounds in the form of ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids, which display surface activity, i.e. they are surfactants. It has been discovered that these compounds function as reactive surfactants, i.e. surface active agents in polymerization processes, particularly emulsion polymerization processes.
  • the surface active agents of the present invention are capable of polymerizing with themselves (to form homopolymeric surface active agents) and/or are capable of co-polymerizing with other ethylenically unsaturated monomers of the type which are commonly employed in polymerization processes.
  • the polymerizable surface active agents utilized in the present invention are prepared from readily available, economical raw materials, and generally, their preparation does not require any special handling or equipment.
  • the surface active agents of the present invention are prepared from readily available, economical raw materials, and generally, their preparation does not require any special handling or equipment.
  • the polymerizable surface active agents may be prepared in a batch mode or a continuous mode; they may be prepared by contacting the ethylenically unsaturated amine with the acid or contacting the acid with the ethylenically unsaturated amine. By contacting it is meant that the acid(s) is added to the ethylenically unsaturated amine(s) and the components are mixed, or the ethylenically unsaturated amine(s) is added to the acid(s) and the components are mixed. Typically, upon mixing, the acid and the base combine to form an amine salt.
  • an improved method for forming agricultural formulations comprising an agricultural technical (i.e. a herbicide, pesticide/insecticide, or fungicide) and latex polymers derived from polymerizable surface active agents detailed herein.
  • an agricultural technical i.e. a herbicide, pesticide/insecticide, or fungicide
  • latex polymers derived from polymerizable surface active agents detailed herein i.e. a herbicide, pesticide/insecticide, or fungicide
  • the improved method comprises: a) preparing a mixture comprising: i) at least one ethylenically unsaturated monomer; ii) at least one polymerizable, surface active agent; wherein the polymerizable, surface active agent is an amine salt or quaternary nitrogen compound comprising: a) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and b) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety; and b) polymerizing the mixture to form a polymer latex; c)adding to the polymer latex an agricultural technical; wherein the polymerizable, surface active agent is capable of polymerization with itself, polymerization with the ethylenically unsaturated monomer or co-polymerization with a partially polymerized polymer particle.
  • the nitrogen atom is linked covalently, directly or indirectly, to the ethylenically unsaturated moiety of the nitrogenous base.
  • the polymerizable surface active agent is in the form of an amine salt, rather than a quaternary nitrogen compound.
  • the agricultural technical may be added before or during the polymerization.
  • the invention relates to agricultural formulations, and in particular to herbicidal, fungicidal and pesticidal/insecticidal compositions for both pre-emergence and post-emergence application.
  • pesticide or pesticidal
  • insecticide or insecticidal
  • the polymers prepared utilizing the polymerizable surface active agents of the present invention may be used as the primary resin component or a minor resin component of a resin mixture which is used to prepare latexes, coatings, adhesives, sealants, elastomers, binders, inks, floor finishes and the like.
  • a polymer is defined herein as a product produced by polymerizing two or more monomers, which may be the same or different. Additionally, the polymer may have inco ⁇ orated into it, surface active agent monomers and/or homopolymeric surface active agents.
  • compositions, application and polymer products described herein may contain various optional ingredients such as fillers, pigments, colorants, solvents, plasticizers, antioxidants, curing agents, thickeners, non-polymerizable surface active agents (surfactants), preservatives, wet strength additives, and the like.
  • optional ingredients such as fillers, pigments, colorants, solvents, plasticizers, antioxidants, curing agents, thickeners, non-polymerizable surface active agents (surfactants), preservatives, wet strength additives, and the like.
  • the present invention provides an improved polymerization process for forming polymers, wherein the polymerizable surface active agent used in the polymerization reaction does not interfere with the quality of the CASE applications or the agricultural formulations.
  • the present invention provides an improved polymerization process, wherein agricultural formulations prepared, using the polymers of the present invention, remain uniform and stable upon the passage of time.
  • the present invention provides polymers suitable for use in coating, adhesive, sealant and/or elastomer (CASE) applications and agricultural formulations.
  • the polymers may be in a variety of forms, such as, for example, solids, flakes, powders, semi-solids, thick pastes, flowable/pumpable pastes (i.e. G-phase pastes), liquids, gels, "ringing" gels, dilute or concentrated solutions and the like.
  • the polymers may be spray dried, flaked, extruded, or the like.
  • the present invention additionally provides homopolymeric surface active agents comprised of polymerized, polymerizable surface active agents or blends of polymerizable surface active agents. These homopolymeric surface active agents are useful in the polymerization processes detailed herein.
  • the present invention further provides homopolymeric surface active agent/polymerizable surface active agent blends comprised of partially polymerized, polymerizable surface active agents and non-polymerized, polymerizable surface active agents. These homopolymeric/polymerizable surface active agent blends are also useful in the polymerization processes detailed herein.
  • the improved polymerization process of the present invention preferably does not require the use of a surfactant which contains residual formaldehyde or other low molecular weight volatile organic compounds.
  • a surfactant which contains residual formaldehyde or other low molecular weight volatile organic compounds.
  • low molecular weight volatile organic compounds and/or residual formaldehyde may be present in the polymerization products of the present invention.
  • the polymerization process of the present invention provides latexes with improved shear stability, improved pH stability, improved shelf storage stability and improved ease of viscosity modification.
  • the polymerizable surface active agent may be added to the mixture in a batch mode
  • a continuous mode i.e. by addition of an amount of the polymerizable surface active agent throughout the polymerization
  • a semi-continuous mode i.e. addition of portions of the polymerizable surface active agent at various times during the polymerization
  • the polymerizable surface active agents utilized in the present invention are generally formed by combining at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, with a nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety.
  • the polymerizable surface active agents of the present invention are preferably in the form of amine salts.
  • the surface active agents of the present invention are prepared from readily available, economical raw materials, and generally, their preparation does not require any special handling or equipment.
  • the polymerizable surface active agents may be prepared in a batch mode or a continuous mode; they may be prepared by contacting the ethylenically unsaturated amine with the acid or contacting the acid with the ethylenically unsaturated amine.
  • contacting it is meant that the acid(s) is added to the ethylenically unsaturated amine(s) and the components are mixed, or the ethylenically unsaturated amine(s) is added to the acid(s) and the components are mixed.
  • the acid and the base combine to form an amine salt.
  • the nitrogenous base becomes a conjugate acid and the acid becomes a conjugate base.
  • the polymerizable surface active agents may alternatively be prepared by contacting the ethylenically unsaturated amine with an alkaline earth or ammonium salt of the acid (e.g., the sodium, potassium, magnesium, calcium, ammonium, or ethoxylated ammonium salts of the acid), whereby the polymerizable surface active agent is formed in situ.
  • an alkaline earth or ammonium salt of the acid e.g., the sodium, potassium, magnesium, calcium, ammonium, or ethoxylated ammonium salts of the acid
  • the surface active agents and blends of surface active agents may be prepared in a variety of forms, including but not limited to, liquids, solutions, solids, powders, flakes, semi- solids, gels, "ringing" gels, G-phase liquids, hexagonal phase solids, or thick pastes.
  • the surface active agents may be spray dried, flaked, extruded, and the like.
  • the polymerizable, surface active agents may be prepared "neat” or in a conventional solvent such as water, low molecular weight alcohol or hydrocarbon, or a mixture thereof, to produce a solution of the surface active agent.
  • the present invention encompasses surface active agents as salts in dry form and as aqueous solutions. Salts of the surface active agents may be isolated by drying a solution of the surface active agents; a solution of surface active agents may be prepared by dissolving the salt of the surface active agent in water, low molecular weight alcohol or hydrocarbon, or a mixture thereof.
  • Individual surface active agents of the present invention may be prepared and mixed together to produce a surface active mixture comprising "neat" surface active agents or an aqueous surfactant blend. Additionally, neat or aqueous blends of the surface active agents may be prepared by contacting a blend of two or more ethylenically unsaturated amines with one acid, or by contacting a blend of two or more ethylenically unsaturated amines with a blend of 2 or more acids.
  • blends of the surface active agents may be prepared by contacting a blend of two or more acids with one ethylenically unsaturated amine, or by contacting a blend of two or more acids with a blend of two or more ethylenically unsaturated amines.
  • a stabilized water dilutable agricultural composition which has been prepared by forming a mixture of a polymer latex and a herbicide, pesticide or fungicide, which is not freely soluble in water but has a water solubility of at least 500 parts per billion by weight, wherein the mixture is generally dilutable in water, at least to a dilution of 50:1 by weight.
  • latex as used herein is intended to include any polymeric product produced as an aqueous suspension emulsion polymerization process and includes within its scope both synthetic latexes and natural latexes.
  • water dilutable as used herein is intended to mean that the agricultural formulation or composition may effectively be diluted in water to any desired dilution e.g. to a dilution of at least 50:1 (wate ⁇ composition) by weight, typical 500:1, without fiocculation or coagulation. In preferred examples of the composition of the invention the water dilutability of the composition is retained, even in the presence of electrolytes, such as ionic fertilizers or pesticides.
  • a method for forming agricultural formulations using latex polymers prepared from monomers and polymerizable surface active agents comprises: (1) preparing a mixture comprising at least one ethylenically unsaturated monomer and at least one polymerizable surface active agent; (2) polymerizing the mixture to form polymer latex; and (3) adding an agricultural technical to the polymer latex.
  • any ethylenically unsaturated monomer that is capable of undergoing polymerization may be utilized in the present invention.
  • the method of the present invention is particularly well suited to emulsion polymerization but may also be conducted as a solution polymerization, suspension polymerization, micro emulsion polymerization or inverse emulsion polymerization.
  • the polymerization may be conducted in any manner known to the art, including but not limited to, free-radical initiated polymerization, thermal initiated polymerization and redox initiated polymerization using, for example, batch, continuous, or controlled monomer feed processes, known conditions of stirring time and temperature, and known kinds of additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents, protective colloids and the like.
  • free-radical initiated polymerization thermal initiated polymerization
  • redox initiated polymerization using, for example, batch, continuous, or controlled monomer feed processes, known conditions of stirring time and temperature, and known kinds of additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents, protective colloids and the like.
  • additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents, protective colloids and the like.
  • the present invention will be carried out from about 20°C to about 120°C (e.g., between about
  • the mixture may be a solution, emulsion, suspension or dispersion of the ethylenically unsaturated monomer and the polymerizable surface active agent.
  • the polymerizable surface active agent may be provided to the mixture as an aqueous solution.
  • the agricultural technical may be added before or during the polymerization.
  • polymerization may occur simultaneously as the mixture is being formed (i.e. as the monomer and the polymerizable surface active agent come in contact, a self-initiating polymerization occurs).
  • the present invention also encompasses a method for continuous polymerization, utilizing at least one ethylenically unsaturated monomer and at least one polymerizable surface active agent.
  • the polymerizable, surface active agents utilized in the present invention are preferably amine salts (or somewhat less preferably quaternary nitrogen compounds) comprising: a) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and b) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety.
  • the polymerizable surface active agents are generally capable of polymerization with themselves, polymerization with the ethylenically unsaturated monomer or co-polymerization with a partially polymerized polymer particle.
  • the polymerizable surface active agent is partially (i.e. 1-50 percent by weight of the polymerizable surface active agent) consumed by polymerization with itself, co- polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.
  • the polymerizable, surface active agent is substantially (i.e. 50-90 percent by weight of the polymerizable surface active agent) consumed by polymerization with itself, co-polymerization with the monomer and/or co- polymerization with a partially polymerized polymer particle.
  • the polymerizable, surface active agent is substantially completely (i.e.
  • the polymerizable surface active agent consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.
  • the polymerizable surface active agent and the ethylenically unsaturated monomer are in a ratio of about 0.01 :1 to about 3:1 on a weight basis, prior to polymerization.
  • the polymerizable surface active agent is present in the mixture in a concentration of about 1-100 weight percent, based on the total weight of the ethylenically unsaturated monomer present in the mixture.
  • the polymerizable surface active agent is present in the mixture in a concentration of about 1-20 weight percent, based on the total weight of the ethylenically unsaturated monomer present in the mixture.
  • the polymerizable surface active agent comprises about 0.1-10 weight percent of the polymer, more preferably 0.5-3.0, based on the total weight of the ethylenically unsaturated monomer present prior to polymerization.
  • the method of preparing polymers in accordance with the present invention does not require the use of a non-polymerizable surfactant, i.e. the mixture is substantially free of non-polymerizable, surface active agents.
  • the mixture further comprises a supplemental, non-polymerizable surfactant (iii); wherein the supplemental surfactant is a sodium, potassium, calcium, magnesium, or ammonium salt of a substantially saturated anionic surfactant, or a nonionic, cationic, or amphoteric surfactant, or a mixture thereof; and wherein the supplemental surfactant is provided in a concentration of about 0.01 to about 20.0 percent by weight, based on the total weight of polymerizable surface active agent and supplemental surfactant provided in the reaction zone.
  • a supplemental, non-polymerizable surfactant a sodium, potassium, calcium, magnesium, or ammonium salt of a substantially saturated anionic surfactant, or a nonionic, cationic, or amphoteric surfactant, or a mixture thereof
  • the supplemental surfactant is provided in a concentration of about 0.01 to about 20.0 percent by weight, based on the total weight of polymerizable surface active agent and supplemental surfactant provided in
  • the present invention provides pre-polymerization mixtures comprising (1) at least one ethylenically unsaturated monomer; (2) at least one polymerizable surface active agent; and (3) an agricultural technical. wherein the ethylenically unsaturated monomer, the polymerizable surface active agent, and the agricultural technical are defined as above or below.
  • This pre-polymerization mixture may be polymerized by a variety of initiation methods known to the art.
  • the present invention provides agricultural formulations comprising an agricultural technical and polymers comprising: (1) at least one monomer unit; and (2) at least one surface active agent unit; wherein the monomer unit is derived from an ethylenically unsaturated monomer; wherein the surface active agent is derived from a polymerizable surface active agent; and wherein the ethylenically unsaturated monomer and the polymerizable surface active agent have co-polymerized to form the polymer.
  • the present invention provides a method for forming agricultural formulations wherein the method comprises (1) preparing a mixture comprising at least one ethylenically unsaturated monomer, at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, and at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety; (2) polymerizing the mixture to form a polymer latex; and (3) adding an agricultural technical to the polymer latex.
  • the acid and the nitrogenous base may form a polymerizable, surface active agent in situ; wherein the polymerizable, surface active agent is an amine salt (or somewhat less preferably a quaternary nitrogen compound); wherein the polymerizable surface active agent is capable of polymerization with itself, copolymerization with the ethylenically unsaturated monomer and/or co-polymerizing with a partially polymerized polymer particle; and wherein the polymerizable, surface active agent is substantially completely consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.
  • the polymerizable, surface active agent is an amine salt (or somewhat less preferably a quaternary nitrogen compound)
  • the polymerizable surface active agent is capable of polymerization with itself, copolymerization with the ethylenically unsaturated monomer and/or co-polymerizing with a partially polymerized polymer particle
  • the nitrogenous base may partially or completely co-polymerize with the ethylenically unsaturated monomer, followed by formation of a surface active agent (i.e. complexation/salt formation with the acid).
  • a surface active agent i.e. complexation/salt formation with the acid.
  • a portion of the nitrogenous base may polymerize with itself, co-polymerizes with the ethylenically unsaturated monomer or co-polymerize with a partially polymerized polymer, followed by complexation/salt formation with the acid.
  • the nitrogenous base may partially or completely co-polymerize with a homopolymeric surfactant, followed by complexation/salt formation with the acid.
  • the present invention provides agricultural formulations comprising an agricultural technical and polymers comprising: (1) at least one monomer unit; (2) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety; wherein the monomer unit is derived from an ethylenically unsaturated monomer; wherein the nitrogenous base is homopolymerized, co-polymerized with the monomer, and/or polymerized with a partially polymerized polymer, wherein the acid complexes to the nitrogen atom(s), to form an amine salt- or a quaternary nitrogen-containing polymer.
  • the present invention provides a method for forming agricultural formulations, wherein the method comprises: (1) preparing a mixture comprising at least one ethylenically unsaturated monomer and at least one homopolymeric surface active agent, the homopolymeric surface active agent being a polymer formed by polymerizing at least one polymerizable, surface active agent; wherein the polymerizable, surface active agent is an amine salt or quaternary nitrogen compound comprising at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, and at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety; (2) polymerizing the mixture to form a polymer latex; and (3) adding an agricultural technical to the polymer latex.
  • the present invention provides homopolymeric surface active agents. These homopolymeric surface active agents are formed by polymerizing at least one polymerizable, surface active agent, wherein the polymerizable, surface active agent is an amine salt or quaternary nitrogen compound comprising at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety.
  • the homopolymeric surface active agents may be formed by partially or completely polymerizing the nitrogenous base, followed by complexation of the resulting polymer with the acid, wherein the acid complexes to the nitrogen atom(s), to form an amine salt- or a quaternary nitrogen-containing homopolymeric surface active agent.
  • the homopolymeric surface active agents of the invention are generally capable of polymerization with themselves, co-polymerization with the monomer or co-polymerization with a partially polymerized polymer.
  • the present invention provides a method for forming agricultural formulations, wherein the method comprises: (1) partially polymerizing at least one ethylenically unsaturated monomer to form a partially polymerized polymer/monomer mixture; (2) adding to the partially polymerized polymer/monomer mixture at least one polymerizable surface active agent and/or at least one homopolymeric surface active agent, to form a partially polymerized polymer/monomer/surface active agent mixture; (3) polymerizing the partially polymerized polymer/monomer/surface active agent mixture to form a polymer latex; and (4) adding an agricultural technical to the polymer latex; wherein the homopolymeric surface active agent being a polymer formed by polymerizing at least one polymerizable, surface active agent; wherein the polymerizable, surface active agent is an
  • the present invention provides a method for forming agricultural formulations, wherein the method comprises: (1) preparing a mixture comprising at least one ethylenically unsaturated monomer and at least one non-polymerizable, supplemental surface active agent; (2) partially polymerizing the mixture to form a partially polymerized polymer/monomer/supplemental surface active agent mixture; (3) adding to the partially polymerized polymer/monomer/supplemental surface active mixture at least one polymerizable surface active agent and/or at least one homopolymeric surface active agent, to form a partially polymerized polymer/monomer/supplemental surface active agent/polymerizable surface active agent mixture; and (4) polymerizing the partially polymerized polymer/monomer/surface active agent/polymerizable surface active agent mixture to form a polymer latex; and (5) adding an agricultural technical to the polymer latex; wherein the homopolymeric surface active agent being a polymer formed by polymerizing at least one polymerizable, surface active agent; wherein the
  • the present invention provides a method for forming agricultural formulations, which contain suspensions or dispersions of polymers of the instant invention, wherein the method comprises: (1) preparing a mixture comprising at least one ethylenically unsaturated monomer and at least one non-polymerizable, supplemental surface active agent; (2) polymerizing the mixture to form a polymer latex; (3) adding at least one polymerizable surface active agent and/or at least one homopolymeric surface active agent to the polymer latex; and (4) adding an agricultural technical to the polymer latex; wherein the homopolymeric surface active agent being a polymer formed by polymerizing at least one polymerizable, surface active agent; wherein the polymerizable, surface active agent is an amine salt or quaternary nitrogen compound comprising at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, and at least one nitrogenous base, wherein the nitrogenous base contains at
  • the present invention encompasses polymers prepared by any of the methods or processes described herein. Generally, the methods of the present invention encompass, emulsions, suspensions or dispersion of polymers obtained therefrom. Ethylenicallv Unsaturated Monomers
  • ethylenically unsaturated monomer or monomers that may be polymerized or copolymerized according to the present invention are known to the art and are described below in a representative manner.
  • suitable ethylenically unsaturated monomers are, for example, mono- and polyunsaturated hydrocarbon monomers, vinyl esters (e.g., vinyl esters of C
  • vinyl esters e.g., vinyl esters of C
  • vinyl ethers e.g.,
  • suitable hydrocarbon monomers for use in the present invention include styrene compounds (e.g., styrene, carboxylated styrene, and alpha-methyl styrene), ethylene, propylene, butylene, and conjugated dienes (e.g., butadiene, isoprene and copolymers of butadiene and isoprene).
  • styrene compounds e.g., styrene, carboxylated styrene, and alpha-methyl styrene
  • ethylene ethylene
  • propylene butylene
  • conjugated dienes e.g., butadiene, isoprene and copolymers of butadiene and isoprene
  • vinyl and vinylidene halides include vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.
  • acrylic esters and methacrylic esters suitable for use in the present invention include C ⁇ -C ⁇ 2 (e.g., C]-C 4 ) alkyl acrylates and methacrylates.
  • Typical alkyl esters and methacrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-dimethylbutyl acrylate, 3,3-dimethyl butyl methacrylate, and lauryl acrylate.
  • Suitable vinyl esters for use in the present invention include aliphatic vinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate, and allyl esters of saturated monocarboxylic acids, such as allyl acetate, allyl propionate and ally lactate.
  • Vinyl ethers suitable for use in the present invention include methylvinyl ether, ethylvinyl ether and n-butylvinyl ether.
  • vinyl ketones include methylvinyl ketone, ethylvinyl ketone and isobutylvinyl ketone.
  • Suitable dialkyl esters of monoethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate, diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and dioctyl itaconate.
  • Monoethylenically unsaturated monocarboxylic acids suitable for use in the present invention include acrylic acid, methacrylic acid, ethacrylic acid, and crotonic acid.
  • Suitable monoethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid.
  • Suitable monoethylenically unsaturated tricarboxylic acids include aconitic acid and the halogen-substituted derivatives (e.g., alphachloracylic acid), and the anhydrides of these acids (e.g., maleic anhydride and citraconic anhydride).
  • Nitriles of the above ethylenically unsaturated mono-, di- and tricarboxylic acids which are suitable monomers include acrylonitrile, alpha-chloroacrylonitrile and methacrylonitrile.
  • Suitable amides of these carboxylic acids include unsubtituted amides such as acrylamide, methacrylamide and other alpha-substituted acrylamides and N-substituted amides obtained by the reaction of the amides of the aforementioned mono- and polycarboxylic acids with and aldehyde (e.g., formaldehyde).
  • Typical N-substituted amides include N-methylolacrylamide, N-methylolmethacrylamide alkylated N-methylolacrylamides and N-methylolmethacrylamides (e.g., N-methyoxymethylacrylamide and N- methoxymethylmethacrylamide).
  • Amino monomers useful in the present invention include substituted and unsubstituted aminoalkyl acrylates, hydrochloride salts of amino monomers and methacrylates, such as beta-aminoethylacrylate, beta-amino-ethylmethacrylate, dimethylaminomethylacrylate, beta- methylaminoethylacrylate, and dimethylaminomethylmethacrylate.
  • Hydroxy-containing monomers useful in the present invention include beta- hydroxyethylacrylate, beta-hydroxypropylacrylate, gamma-hydroxypropylacrylate and beta- hydroxyethylmethacrylate.
  • Monomers useful in the present invention may be homopolymerized or copolymerized, i.e., one or more different monomers capable of polymerization may be used.
  • the polymerizable surface active agents utilized in the present invention are amine salts or quaternary nitrogen compounds comprising at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, and at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least on ethylenically unsaturated moiety.
  • the polymerizable surface active agents used are in the form of amine salts.
  • the polymerizable surface active agents is usually present in the mixture in a concentration from about 0.01-100.0 percent by weight based on the total weight of the ethylenically unsaturated monomer.
  • the polymerizable surface active agents have a hydrophilic/lipophilic balance (HLB) of less than about 45. In a somewhat more prefened embodiment, the polymerizable surface active agents have an HLB of about 5-40.
  • the polymerizable surface active agents are generally capable of polymerization with themselves, co-polymerization with the ethylenically unsaturated monomer, or co-polymerization with a partially polymerized polymer.
  • the polymerizable surface active agents of the present invention are prepared from readily available, economical raw materials, and generally, their preparation does not require any special handling or equipment.
  • the polymerizable surface active agents may be prepared in a batch mode or a continuous mode; they may be prepared by contacting nitrogenous base with the acid or contacting the acid with the nitrogenous base. By contacting it is meant that the acid(s) is added to the nitrogenous base and the components are mixed, or the ethylenically unsaturated amine(s) is added to the acid(s) and the components are mixed.
  • the surface active agents and blends of surface active agents may be prepared in a variety of forms such as, for example, liquids, solutions, solids, powders, flakes, semi-solids, gels, "ringing" gels, G-phase liquids, hexagonal phase solids, or thick pastes.
  • the surface active agents may be spray dried, flaked, extruded, and the like.
  • the polymerizable surface active agents may be prepared "neat” or in a conventional solvent such as water, low molecular weight alcohol or hydrocarbon, or a mixture thereof, to produce a solution of the polymerizable surface active agent.
  • the present invention encompasses polymerizable surface active agents as salts in dry form and as aqueous solutions.
  • the polymerizable surface active agents may be isolated by drying a solution of the surface active agents; a solution of polymerizable surface active agents may be prepared by dissolving a solid form of the polymerizable surface active agent (i.e. an amine salt) in water, low molecular weight alcohol or hydrocarbon, or a mixture thereof.
  • Polymerizable surface active agents of the present invention may be prepared and mixed together to produce a surface active mixture comprising "neat" surface active agents or an aqueous surfactant blend.
  • neat or aqueous blends of the polymerizable surface active agents may be prepared by contacting a blend of two or more nitrogenous bases with one acid, or by contacting a blend of two or more nitrogenous bases with a blend of 2 or more acids.
  • blends of the polymerizable surface active agents may be prepared by contacting a blend of two or more acids with one nitrogenous base, or by contacting a blend of two or more acids with a blend of two or more nitrogenous bases.
  • the polymerizable surface active agents utilized in the present invention may be homopolymerized (i.e. polymerized with themselves), or partially homopolymerized, prior to use in the polymerization, to form a homopolymeric surface active agent or a blend of homopolymeric surface active agent(s) and polymerizable surface active agents.
  • the acids useful in the present invention are generally sulfonic acids, polysulfonic acids, sulfonic acids of oils, paraffin sulfonic acids, lignin sulfonic acids, petroleum sulfonic acids, tall oil acids, olefin sulfonic acids, hydroxyolefm sulfonic acids, polyolefm sulfonic acids, polyhydroxy polyolefm sulfonic acids, carboxylic acids, perfluorinated carboxylic acids, carboxylic acid sulfonates, alkoxylated carboxylic acid sulfonic acids, polycarboxylic acids, polycarboxylic acid polysulfonic acids, alkoxylated polycarboxylic acid polysulfonic acids, phosphoric acids, alkoxylated phosphoric acids, polyphosphoric acids, and alkoxylated polyphosphoric acids, fluorinated phosphoric acids, phosphoric acid esters of oils, phosphinic acids, alkyl
  • acids phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters, ⁇ -phosphono fatty acids, oragnoamine polymethylphosphonic acids, organoamino dialkylene phosphonic acids, alkanolamine phosphonic acids, trialkyledine phosphonic acids, acylamidomethane phosphonic acids, alkyliminodimethylene diphosphonic acids, polymethylene-bis(nitrilo dimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene) amine oxide acids, esters of substituted aminomethylphosphonic acids, phosphonamidic acids, acylated amino acids
  • N-alkyl acylamino acids e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids
  • N-alkyl acylamino acids e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids
  • N-alkyl acylamino acids e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids
  • N-alkyl acylamino acids e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids
  • N-alkyl acylamino acids e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids
  • acids which are useful in the present invention are selected from the group comprising linear or branched alkylbenzene sulfonic acids, alkyl sulfuric acid esters,
  • alkoxylated alkyl sulfuric acid esters ⁇ -sulfonated alkyl ester acids, ⁇ -sulfonated ester
  • sulfonic acids perfluorinated alkyl sulfonic acids, sulfosuccinic mono- and diester acids, polysulfosuccinic polyester acids, sulfoitaconic diester acids, sulfosuccinamic acids, sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids, sulfophthalic acids, sulfoisophthalic acids, phthalamic acids, sulfophthalamic acids, alkyl ketone sulfonic acids, hydroxyalkane- 1 -sulfonic acids, lactone sulfonic acids, sulfonic acid amides, sulfonic acid diamides, alkyl phenol sulfuric acid esters, alkoxylated alkyl phenol sulfuric acid esters, alkylated cycloalkyl sulfuric acid esters, alkoxylated alkylated cycloal
  • suitable acids of the present invention include fluorinated carboxylic acids, fluorinated sulfonic acids, fluorinated sulfate acids, fluorinated phosphonic and phosphinic acids, and mixtures thereof.
  • the sulfuric acid esters are preferably immediately converted to ethylenically unsaturated amine salts.
  • linear dodecyl alcohol is sulfated with SO 3 to produce an intermediate, hydrolytically unstable, dodecyl alcohol sulfate acid as shown in Scheme I below.
  • the intermediate acid is neutralized with an ethylenically unsaturated nitrogenous base, such as allyl amine, to produce a dodecyl sulfate ethylenically unsaturated amine salt.
  • methyl laurate is sulfonated with SO to produce an
  • an ethylenically unsaturated nitrogenous base such as allyl amine
  • an ⁇ -sulfonated lauryl methyl ester ethylenically unsaturated amine di-salt may
  • unsaturated amine di-salt may be formed as a mixture depending on the sulfonation conditions employed. The ratio of unsaturated amine salt to unsaturated amine di-salt is readily controlled by sulfonation conditions, well known to those skilled in the art.
  • Ethylenically unsaturated amine salts of sulfosucinnate ester acids are typically produced by sulfitation of a succinic acid alkyl diester with sodium bisulfite, followed by, for example, ionic exchange with an ethylenically unsaturated nitrogenous base, such as allyl amine, as shown in Scheme IV below.
  • the sarcosinic acid ethylenically unsaturated amine salts are prepared by the amidation of a fatty acid, a fatty acid alkyl ester or a fatty acid chloride with sarcosine, followed by addition of an ethylenically unsaturated nitrogenous base, such as allyl amine, as shown in Scheme V below.
  • an ethylenically unsaturated nitrogenous base such as allyl amine
  • the ethylenically unsaturated nitrogenous base is combined with sarcosine to produce the conesponding sarcosine salt, which is then be used to amidate the fatty acid, fatty acid alkyl ester or fatty acid chloride.
  • the isethionic acid ethylenically unsaturated amine salts may be prepared by the esterification of a fatty acid, a fatty acid alkyl ester or a fatty acid chloride with isethionic acid, followed by addition of an ethylenically unsaturated nitrogenous base, such as allyl amine, as shown in Scheme VI below. Additionally, isethionic acid ethylenically unsaturated amine salts may be prepared by esterifying a fatty acid, a fatty acid alkyl ester or a fatty acid chloride with the sodium salt of isethionic acid, followed by ion exchange with the ethylenically unsaturated nitrogenous base, such as allyl amine.
  • isethionic acid or its sodium salt
  • the ethylenically unsaturated nitrogenous base such as allyl amine
  • isethionic acid allyl amine salt which may then be esterified with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the prefened acids of the present invention are branched or linear alkylbenzene
  • alkyl ester acids fatty carboxylic acids and phosphoric acid esters, and mixtures thereof.
  • the most prefened acids of the present invention are branched or linear alkylbenzene sulfonic acids, alkyl sulfuric acid esters, and alkoxylated alkyl sulfuric acid esters, and mixtures thereof.
  • sulfonic acid salts of ethylenically unsaturated amines include sultone precursors, such as cyclic alkyl sultones.
  • sultone-derived sulfonic acid salts include 2-acetamidoalkyl-l -sulfonates and amino carboxy acid alkyl sulfonates, as shown in Scheme VII and Scheme VIII below.
  • R is C -24 alkyl
  • nitrogenous bases which are useful in the present invention are any nitrogenous base which contains an ethylenically unsaturated moiety, including various vinyl amines.
  • the nitrogenous base useful in accordance with the present invention is a compound of the formula
  • R ⁇ , R 2 and R are independently hydrogen or organic groups containing an ethenylene group, provided that at least one of R]-R is a straight or branched chain alkyl group containing 1-8 carbon atoms and an ethenylene functionality.
  • nitrogenous bases that are useful in the present invention are ethylenically unsaturated amines selected from the group comprising vinyl amine, N-methyl N-allyl amine, C ⁇ -C 24 alkyl allyl amine, C ⁇ -C 24 alkyl ethoxylated and/or propoxylated allyl amine, C ⁇ -C 2 dialkyl allyl amine, ethoxylated and/or propoxylated allyl amine diallyl amine, C ⁇ -C 24 alkyl diallyl amine, ethoxylated and/or propoxylated diallyl amine, triallyl amine, 1 ,2-diaminoethene, aminocrotonitrile, diaminomaleonitrile, N- allylcyclopentylamine, N-allylaniline, allylcyclohexylamine, [l-(2-allylphenoxy)-3- (isopropylamino)-2-propanol],
  • More prefened nitrogenous bases of the present invention are allyl amine, diallyl amine, triallyl amine, methylallyl amine, N-allyl-N,N-dimethyl amine, methyl 3-amino crotonate, 3-amino crotononitrile, 3-amino- 1-propanol vinyl ether, N-methyl N-allyl amine, 2- (dimethylamino)ethyl acrylate, or l,4-diamino-2-butene, and mixtures thereof.
  • the most prefened nitrogenous bases of the present invention are allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, and 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • amine salts are generally prefened over quaternary ammonium compounds.
  • Ri is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms
  • Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, or a mixture thereof
  • M + is a conjugate acid of the nitrogenous base
  • n is an integer of from 1-5 and m is an integer of from 1-8; and wherein the total number of carbon atoms represented by (R ⁇ ) n is at least 5.
  • Ri is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • Ar is a phenyl
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof and n is 1 and m is 1.
  • the surface active agent is of the formula:
  • nl 4 -18; and wherein R' is hydrogen or saturated or unsaturated hydrocarbon group having from about 1 -8 carbon atoms.
  • the present invention further utilizes surface active agents of the formula (R 1 ) n ,- ⁇ Ar(SO 3 -M + ) ml ⁇ -O- ⁇ Ar(SO 3 -M + ) m2 ⁇ -(R 2 ) n2 wherein R] and R 2 are independently hydrogen, or saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, or a mixture thereof; wherein M + is a conjugate acid of the nitrogenous base; wherein nl and n2 are independently 0-5, provided that nl and n2 are not both equal to zero; and wherein ml and m2 are independently 0-8, provided that ml and m2 are not both equal to zero.
  • Ri is hydrogen and R is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • Ar is phenyl
  • R ⁇ and R are independently saturated or unsaturated hydrocarbon groups having from about 6-24 carbon atoms
  • Ar is phenyl
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N- allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof, nl and n2 both equal one, and ml and m2 both equal one.
  • the surface active agent is of the formula:
  • n and n' are independently 4-18; and wherein R' and R" are independently hydrogen, methyl, ethyl or propyl.
  • the present invention further utilizes surface active agents of the formula:
  • R ⁇ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • R 2 is methyl, ethyl, or propyl, or a mixture thereof
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • the surface active agent is of the formula:
  • n 3-18.
  • the present invention further utilizes surface active agents of the formula:
  • R ⁇ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N- methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • the surface active agent is of the formula:
  • n 3-18.
  • the present invention further utilizes surface active agents of the formula: R,-CH(SO 3 " M + )C(O)O(CH 2 CH(R')O)n R 2 wherein R ⁇ and R 2 are independently saturated or unsaturated hydrocarbon groups having from about 1- 24 carbon atoms; wherein R' is methyl or hydrogen; wherein n is an integer of from 1-100; and wherein M + is a conjugate acid of the nitrogenous base.
  • Ri is a saturated or unsaturated hydrocarbon group having from about 4-24 carbon atoms
  • R' is methyl or hydrogen
  • R 2 is methyl, ethyl, or propyl
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof
  • n 1-100.
  • the surface active agent is of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • R ⁇ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • the surface active agent is of the formula:
  • n 5-17.
  • the present invention further utilizes surface active agents of the formula:
  • R CO 2 (CH 2 ) n CH(SO 3 ' M + )CO 2 R 2 wherein Ri and R 2 are independently saturated or unsaturated hydrocarbon groups having from about 1- 24 carbon atoms; wherein n is zero or an integer of from 1-10; and wherein M + is a conjugate acid of the nitrogenous base.
  • the surface active agent is of the formula:
  • nl is zero or an integer of from 1- 17
  • the present invention further utilizes surface active agents of the formula:
  • R,CO 2 (CH 2 ) n SO 3 " M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1- 24 carbon atoms; wherein n 1-10; and wherein M + is a conjugate acid of the nitrogenous base.
  • the surface active agent is of the formula:
  • nl 2 -18.
  • is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • Ar is phenyl
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof
  • n
  • the surface active agent is of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • R ⁇ is a saturated or unsaturated hydrocarbon group having from about 6- 24 carbon atoms
  • R' is methyl or hydrogen
  • n 0- 100
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • the surface active agent is of the formula:
  • the surface active agent is of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • R,CO 2 Tvl + wherein R
  • R] is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms
  • M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.
  • the surface active agent is of the formula:
  • n 5-18.
  • the present invention further utilizes surface active agents of the formula:
  • the surface active agent is of the formula:
  • nl 2-18.
  • the present invention further utilizes surface active agents of the formula:
  • R CON(R')(CH 2 ) n SO 3 M + wherein R
  • is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R' is methyl, ethyl, propyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; and wherein n 1-10.
  • the surface active agent is of the formula:
  • nl 2-18.
  • the present invention further utilizes surface active agents of the formula:
  • R O(CH 2 CH(R')O) n COCH 2 SO 3 " M + wherein R
  • is a saturated or unsaturated hydrocarbon group having from about 1- 24 carbon atoms; wherein R' is methyl or hydrogen; wherein n 0-100; wherein M + is a conjugate acid of the nitrogenous base.
  • the surface active agent is of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • the present invention further utilizes surface active agents of the formula:
  • R is a saturated or unsaturated hydrocarbon group having from about 1- 24 carbon atoms; wherein Ar is phenyl; wherein R' is methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-
  • polymerizable surface active agents which are quaternary ammonium salts of the general formula:
  • , R 2 , R 3 , and R 4 are independently, substituted or unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon atoms, or hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R 1 -R groups contains at least one or more ethenylene groups; and wherein X " is an anion group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.
  • useful polymerizable surface active agents include those of the above general formula in the form of ring structures formed by covalently linking two of the R ! -R groups.
  • examples include unsaturated imidazolines, imidazoliniums, and pyridiniums, and the like.
  • These quaternary ammonium salts may be prepared by a variety of methods known to the art, for example, halide exchange, wherein a halide based quaternary ammonium compound is ion exchanged with X " , where X " is defined above.
  • the present invention encompasses amine oxide-derived polymerizable surface active agents, formed as shown in Scheme IX, wherein Ri, R 2 , R are independently, substituted or unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon atoms, or hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R ⁇ -R groups contains at least one or more ethenylene groups; and wherein X " is an anion group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.
  • useful polymerizable surface active agents include those of the above general formula in the form of ring structures formed by covalently linking two of the R1-R groups. Examples include unsaturated imidazolines, imidazoliniums, and pyridiniums, and the like.
  • the present invention further encompasses quaternary halide-derived polymerizable surface active agents, formed as shown in Scheme X, wherein R ⁇ , R 2 , R 3 are independently, substituted or unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon atoms, or hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R ⁇ -R 3 groups contains at least one or more ethenylene groups; and wherein X " is an anion group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.
  • useful polymerizable surface active agents include those of the above general formula in the form of ring structures formed by covalently linking two of the Ri-Ri groups. Examples include unsaturated imidazolines, imidazoliniums, and pyridiniums, and the like.
  • the present invention further encompasses polymerizable onium compounds, particularly ammonium salts, sulfonium salts, sulfoxonium salts, oxonium salts, nitronium salts, and phosphonium salts of various anions, including for example, anions group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, acetate and various halides; wherein the onium compound contains at least one ethenylene functionality.
  • onium compounds particularly ammonium salts, sulfonium salts, sulfoxonium salts, oxonium salts, nitronium salts, and phosphonium salts of various anions, including for example, anions group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, n
  • Reverse polymerizable surface active agents utilized in the present invention may be “reverse" polymerizable surface active agents.
  • Reverse polymerizable surface active agents utilized in the present invention are amine salts or quaternary nitrogen compounds comprising: (1) at least one ethylenically unsaturated acid, wherein the acid contains at least one ethylenically unsaturated moiety and is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and (2) at least one substantially saturated nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and a C ⁇ -C 24 alkyl group.
  • substantially saturated nitrogenous base it is meant that the nitrogenous base contains less than about 5% unsaturation in the alkyl group(s).
  • the ethylenically unsaturated acids of the present invention are any sulfonic acids, carboxylic acids, or phosphoric acids which contain at least one unsaturated moiety.
  • the ethylenically unsaturated acids useful in the present invention are generally vinyl sulfonic acids, vinyl sulfmic acids, vinyl sulfenic acids, vinyl sulfonic acid esters, vinyl carboxylic acids, vinyl, phosphoric acids, vinyl phosphonic acids, vinyl phosphinic, vinyl phosphenic acids, unsaturated sulfonic acids, unsaturated polysulfonic acids, unsaturated sulfonic acids of oils, unsaturated paraffin sulfonic acids, unsaturated lignin sulfonic acids, unsaturated petroleum sulfonic acids, unsaturated tall oil acids, unsaturated olefin sulfonic acids, unsaturated hydroxyolefm sulfonic acids, unsaturated polyolefm sulfonic acids, unsaturated polyhydroxy polyolefm sulfonic acids, unsaturated carboxylic acids, unsaturated perfluorinated carboxylic acids, unsaturated carboxylic
  • alkyl esters unsaturated ⁇ -phosphono fatty acids, unsaturated oragnoamine
  • polymethylphosphonic acids unsaturated organoamino dialkylene phosphonic acids, unsaturated alkanolamine phosphonic acids, unsaturated trialkyledine phosphonic acids, unsaturated acylamidomethane phosphonic acids, unsaturated alkyliminodimethylene diphosphonic acids, unsaturated polymethylene-bis(nitrilodimethylene)tetraphosphonic acids, unsaturated alkyl bis(phosphonoalkylidene) amine oxide acids, unsaturated esters of substituted aminomethylphosphonic acids, unsaturated phosphonamidic acids, unsaturated acylated amino acids (e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids), unsaturated N-alkyl acylamino acids, and unsaturated acylated protein hydrolysates, and mixtures thereof.
  • unsaturated organoamino dialkylene phosphonic acids unsaturated alkan
  • ethylenically unsaturated acids which are useful in the present invention are selected from the group comprising unsaturated linear or branched alkylbenzene sulfonic acids, unsaturated alkyl sulfuric acid esters, unsaturated alkoxylated alkyl sulfuric acid esters,
  • alkoxylated ⁇ -sulfonated alkyl ester acids unsaturated ⁇ -sulfonated dialkyl diester acids
  • unsaturated primary and secondary alkyl sulfonic acids unsaturated perfluorinated alkyl sulfonic acids, unsaturated sulfosuccinic mono- and diester acids, unsaturated polysulfosuccinic polyester acids, unsaturated sulfoitaconic diester acids, unsaturated sulfosuccinamic acids, unsaturated sulfosuccinic amide acids, unsaturated sulfosuccinic imide acids, unsaturated phthalic acids, unsaturated sulfophthalic acids, unsaturated sulfoisophthalic acids, unsaturated phthalamic acids, unsaturated sulfophthalamic acids, unsaturated alkyl ketone sulfonic acids, unsaturated hydroxyalkane-1 -sulfonic acids, unsaturated lactone sulfonic acids, unsaturated sulfonic acid amides, unsaturated sulfonic acid di
  • suitable ethylenically unsaturated acids of the present invention include unsaturated fluorinated carboxylic acids, unsaturated fluorinated sulfonic acids, unsaturated fluorinated sulfate acids, unsaturated fluorinated phosphonic and phosphinic acids, and mixtures thereof.
  • the substantially saturated nitrogenous bases of the present invention are any bases which contain at least one nitrogen atom, and are capable of forming a salt with the ethylenically unsaturated acid.
  • the saturated nitrogenous bases suitable for use in the present invention include any primary, secondary or tertiary amine, which has at least one C ⁇ -C 2 alkyl group.
  • the alkyl groups of such amines have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted.
  • Such amines include for example, stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N- tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine and mixtures thereof.
  • auxiliary polymerizable surface active agents i.e. polymerizable surface active agent known to those skilled in the art, in combination with the polymerizable surface active agents, homopolymeric surface active agents, and supplemental surface active agents described herein.
  • Examples of auxiliary polymerizable surface active agents useful in the present invention are shown below in Table I.
  • auxiliary polymerizable surfactants useful herein are generally disclosed in Polymerizable Surfactants Guyot, A. Current Opinions in Colloid and Surface Science, 1996, pg. 580-585; Reactive Surfactants in Emulsion Polymerization Guyot, A.; et. al; Advances in Polymer Science, Vol. 11, Springer-Verlag, Berlin, 1994, pg.43-65; and Polymerizable Surfactant, Holmberg, K., Progress in Organic Coatings, 20 (1992) 325-337 (all inco ⁇ orated herein in their entirety).
  • non-polymerizable surface active agents may be utilized in the present invention.
  • supplemental surfactants are generally combined with the agricultural technical to for the oil phase of the formulation.
  • the supplemental surface active agents are generally anionic, nonionic, cationic or amphoteric surfactants or mixtures thereof, and are typically used as in a concentration of about 0.01 to about 20.0 percent by weight, based on the total weight of surface active agents (i.e. both polymerizable and non- polymerizable). Somewhat more preferably, the supplemental surface active agents are used in a concentration of about 0.01 to about 5.0 percent by weight, based on the total weight of surface active agents (i.e. both polymerizable and non-polymerizable).
  • Suitable supplemental nonionic surface active agents are generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column, 13 line 14 through column 16, line 6, inco ⁇ orated herein by reference.
  • the supplemental nonionic surface active agent is selected from the group comprising polyoxyethylenated alkylphenols, polyoxyethyleneated straight chain alcohols, polyoxyethyleneated branched chain alcohols, polyoxyethyleneated polyoxypropylene glycols, polyoxyethyleneated mercaptans, fatty acid esters, glyceryl fatty acid esters, polyglyceryl fatty acid esters, propylene glycol esters, sorbitol esters, polyoxyethyleneated sorbitol esters, polyoxyethylene glycol esters, polyoxyethyleneated fatty acid esters, primary alkanolamides, ethoxylated primary alkanolamides, secondary alkanolamides, ethoxylated secondary alkanolamides, tertiary acetylenic glycols, polyoxyethyleneated silicones, N-alkylpynolidones, alkylpolyglycosides, alkylpolylsaccharides, EO-PO
  • the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are prefened. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight or branched chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 1 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type are commercially available nonionic surfactants of this type
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contain from about 8 to about 22 carbon atoms. Particularly prefened are the condensation products of alcohols having an alkyl group containing from about 6 to about 11 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially
  • nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation
  • NMW the condensation products of C ⁇ 2 -C ⁇ 4 primary alcohol with 6 moles of ethylene oxide with a nanow molecular weight distribution
  • Neodol® 91-8 (the condensation product of C 9 -Cn linear alcohol with 8
  • Neodol® 23-6.5 the condensation product of Cj 2 -C 13 linear alcohol with 6.5 moles of ethylene oxide
  • Neodol® 45-7 the condensation product of
  • Neodol® 91-6 the condensation product of C 9 -Cn linear alcohol with 6 moles of ethylene oxide
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1880 and exhibits water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which conesponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the
  • Pluronic® surfactants commercially available Pluronic® surfactants, marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40 % to about 80 % by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF.
  • Semi-polar nonionic surfactants are a special category of supplemental nonionic surface active agents which include water-soluble amine oxides containing on alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group comprising alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing alkyl moieties of from about 10 to about 18 carbon atoms and a moiety selected from the group comprising alkyl groups and hydroxyalkyl groups of from about 1 to about 3 carbon atoms.
  • hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglucoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • An ethyl ester ethoxylate and/or alkoxylate such as those described in U.S. Pat. No. 5,220,046, inco ⁇ orated herein by reference. These material may be prepared according to the procedure set forth in Japanese Kokai patent application No. HEI 5 [1993J-222396. For example, they may be prepared by a one-step condensation reaction between an alkyl ester and an alkylene oxide in the present of a catalytic amount of magnesium together with another ion selected from the group of
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from about 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to 3, most preferably from about
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1- position).
  • the additional glucosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4-, and/or 6-position, preferably predominately the 2-position.
  • Suitable supplemental amphoteric surface active agents are selected from the group comprising alkyl glycinates, propionates, imidazolines, amphoalkylsulfonates sold
  • amphoteric surfactants include cocoamphoglycinate, cocoamphocarboxyglycinate, lauramphocarboxyglycinate, cocoamphopropionate, lauramphopropionate, stearamphoglycinate, cocoamphocarboxy-propionate, tallowamphopropionate, tallowamphoglycinate, oleoamphoglycinate, caproamphoglycinate, caprylamphopropionate, caprylamphocarboxyglycinate, cocoyl imidazoline, lauryl imidazoline, stearyl imidazoline, behenyl imidazoline, behenylhydroxyethyl imidazoline, caprylamphopropylsulfonate, cocamphopropylsulfonate, stearamphopropyl-sulfonate, oleoamphopropylsulfonate and the like.
  • supplemental amine oxide surface active agents which are generally suitable for use in the present invention are alkylamine and amidoamine oxides.
  • supplemental betaine and sultaine surface active agents which are suitable for use in the present invention
  • supplemental betaines and sultaines are cocobetaine, cocoamidoethyl betaine, cocoamidopropyl betaine, lauryl betaine, lauramidopropyl betaine, palmamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, coco-sultaine, lauryl sultaine, tallowamidopropyl hydroxysultaine and the like.
  • supplemental cationic surface active agents useful in the present invention are fatty amine salts, fatty diamine salts, polyamine salts, quaternary ammonium compounds, polyoxyethyleneated fatty amines, quaternized polyoxyethyleneated fatty amines, amine oxides and mixtures thereof.
  • Suitable supplemental cationic surface active agents are disclosed in the following documents, all inco ⁇ orated by reference herein: M. C. Publishing Co., McCutcheon 's Detergents & Emulsifiers, (North American Ed., 1993); Schwartz et al., Surface Active Agents, Their Chemistry and Technology, New York; Interscience Publisher, 1949; U.S. Pat. No. 3,155,591, Spotifyr, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey et al., issued May 25, 1976; and U.S. Pat. No.
  • supplemental cationic surface active agents in the form of quaternary ammonium salts include dialkyldiethyl ammonium chlorides and trialkyl methyl ammonium chlorides, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids yield quaternary compounds wherein Ri and R 2 have predominately from about 16 to about 18 carbon atoms).
  • supplemental quaternary ammonium salts useful herein include ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di-(hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, di-(hydrogenated tallow) dimethyl ammonium acetate, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyol ammonium acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium nitrate, di- (coconutalkyl) dimethyl ammonium chloride, and stearyl dimethyl benzyl ammonium chloride.
  • Salts of primary, secondary and tertiary fatty amines are also suitable supplemental cationic surface active agents.
  • the alkyl groups of such supplemental amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted.
  • Such amines useful herein, include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine.
  • Suitable supplemental amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts.
  • Such supplemental salts include stearylamine hydrogen chloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate.
  • Supplemental cationic amine surfactants included among those useful in the present invention are also disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued June 23, 1981, inco ⁇ orated herein by reference.
  • Supplemental cationic surface active agents which are especially useful are quaternary ammonium or amino compounds having at least one N-radical containing one or more nonionic hydrophilic moieties selected from the group comprising alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof.
  • the compounds contain at least one hydrophilic moiety within 4, preferably within 3, carbon atoms (inclusive) of the quaternary nitrogen or cationic amino nitrogen.
  • carbon atoms that are part of a hydrophilic moiety e.g., carbon atoms in a hydrophilic polyoxyalkylene (e.g.,-CH 2 -CH 2 -O-), that are adjacent to other hydrophilic moieties are not counted when determining the number of hydrophilic moieties within 4, or preferably 3, carbon atoms of the cationic nitrogen.
  • the alkyl portion of any hydrophilic moiety is preferably a C
  • Suitable hydrophile-containing radicals include, for example, ethoxy, propoxy, polyoxyethylene, polyoxypropylene, ethylamido, propylamido, hydroxymethyl, hydroxyethyl, hydroxypropyl, methyl ester, ethyl ester, propyl ester, or mixtures thereof, as nonionic hydrophile moieties.
  • supplemental cationic surface active agents useful herein are those of the general formula:
  • Ri, R 2 , R , and R 4 comprise, independently, substituted or unsubstituted substantially saturated hydrocarbyl chains of from about 1 to about 30 carbon atoms, or a hydrocarbyl having from about 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least on of the R ⁇ -R groups contains one or more hydrophilic moieties selected from the group comprising alkoxy (preferably C ⁇ -C 3 alkoxy), polyoxyalkylene (preferably Ci- C polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester and combination thereof.
  • alkoxy preferably C ⁇ -C 3 alkoxy
  • polyoxyalkylene preferably Ci- C polyoxyalkylene
  • alkylamido hydroxyalkyl, alkylester and combination thereof.
  • the cationic conditioning surfactant contains from about 2 to about 10 nonionic hydrophile moieties located within the about stated ranges.
  • each hydrophilic amido, alkoxy, hydroxyalkyl, alkylester, alkylamido or other unit is considered to be a distinct nonionic hydrophile moiety.
  • X " is a substantially saturated soluble salt forming anion preferably selected from the group comprising halogens (especially chlorine), acetate, phosphate, nitrate, sulfonate, and alkyl sulfate radicals.
  • Prefened supplemental cationic surface active agents include polyoxyethylene (2) stearyl methyl ammonium chloride, methyl bis-(hydrogenated tallowamidoethyl) 2- hydroxyethyl ammonium methyl sulfate, polyoxypropylene (9) diethyl methyl ammonium chloride, tripolyoxyethylene (total PEG-10) stearyl ammonium phosphate, bis-(N- hydroxyethyl-2-oleyl imidazolinium chloride) polyethylene glycol (1), and isododecylbenzyl triethanolammonium chloride.
  • supplemental ammonium quaternary and amino surface active agents include those of the above general formula in the form of ring structures formed by covalently linking two of the radicals. Examples include imidazolines, imidazoliniums, and pyridiniums, etc., wherein said compound has at least one nonionic hydrophile-containing radical as set forth above.
  • the alkyl groups of such amines preferably have from about 1 to about 30 carbon atoms and must contain at least one, preferably about 2 to about 10, nonionic hydrophilic moieties selected from the group comprising alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester groups, and mixtures thereof.
  • supplemental anionic surface active agents suitable for use in the present invention are generally the sodium, potassium, calcium, ammonium or alkanolamine salts of any substantially saturated sulfonic acid, carboxylic acid, or phosphoric acid, or a mixture thereof. More specifically, supplemental anionic surface active agents suitable for use in the present invention are generally the sodium, potassium, calcium, ammonium or alkanolamine salts of saturated sulfonic acids, sulfinic acids, sulfenic acids, sulfonic acid esters, carboxylic acids, phosphonic acids, phosphinic, phosphenic acids, polysulfonic acids, sulfonic acids of oils, paraffin sulfonic acids, lignin sulfonic acids, petroleum sulfonic acids, tall oil acids, olefin sulfonic acids, hydroxyolefm sulfonic acids, polyolefm sulfonic acids, polyhydroxy polyolefm sulfonic acids,
  • fatty acids oragnoamine polymethylphosphonic acids, organoamino dialkylene phosphonic acids, alkanolamine phosphonic acids, trialkyledine phosphonic acids, acylamidomethane phosphonic acids, alkyliminodimethylene diphosphonic acids, polymethylene- bis(nitrilodimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene) amine oxide acids, esters of substituted aminomethylphosphonic acids, phosphonamidic acids, acylated amino acids (e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic acids to produce N-acylamino acids), N-alkyl acylamino acids, and acylated protein hydrolysates, and mixtures thereof.
  • organoamino dialkylene phosphonic acids alkanolamine phosphonic acids, trialkyledine phosphonic acids, acylamidomethane phosphonic acids, alkylimino
  • supplemental anionic surface active agents suitable for use in the present invention are the sodium, potassium, calcium, ammonium or alkanolamine salts of saturated linear or branched alkylbenzene sulfonic acids, alkyl sulfuric acid esters, alkoxylated alkyl
  • diester acids ⁇ -sulfonated alkyl acetate acids, primary and secondary alkyl sulfonic acids,
  • perfluorinated alkyl sulfonic acids perfluorinated alkyl sulfonic acids, sulfosuccinic mono- and diester acids, polysulfosuccinic polyester acids, sulfoitaconic diester acids, sulfosuccinamic acids, sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids, sulfophthalic acids, sulfoisophthalic acids, phthalamic acids, sulfophthalamic acids, alkyl ketone sulfonic acids, hydroxyalkane-1- sulfonic acids, lactone sulfonic acids, sulfonic acid amides, sulfonic acid diamides, alkyl phenol sulfuric acid esters, alkoxylated alkyl phenol sulfuric acid esters, alkylated cycloalkyl sulfuric acid esters, alkoxylated al
  • supplemental anionic surface active agents suitable for use in the present invention are generally the sodium, potassium, calcium, ammonium or alkanolamine salts of saturated fluorinated carboxylic acids, fluorinated sulfonic acids, fluorinated sulfate acids, fluorinated phosphonic and phosphinic acids, and mixtures thereof.
  • the polymerization process is conducted in the absence of any non-polymerizable, supplemental surfactant, as the polymerizable surface active agents of the present invention display excellent capacity for producing emulsion stability characteristics in an emulsion polymerization.
  • the polymerizable surface active agents of the present invention may be used as co-monomers with the ethylenically unsaturated monomer(s) to modify the physical properties of the resulting polymer.
  • supplemental surface active agents also may be used as additives to the polymerization, e.g., in amounts of from about 3 to 6 weight percent, based on the total weight of monomer.
  • any conventional organic solvent which may be a solvent for both the monomer(s) and/or polymer, or just the monomer(s) may be used.
  • Organic or inorganic initiators may be used to initiate the polymerization reaction.
  • a sufficient quantity of a polymerization initiator (such as a conventional free radical initiator) is typically introduced into the polymerization medium to cause polymerization of the monomer(s) at the particular temperatures employed.
  • Initiators used in polymerization processes may be of the type which produce free radicals and conveniently are peroxygen compounds, for example: inorganic peroxides such as hydrogen peroxide and inorganic persulfate compounds such as ammonium persulfate, sodium persulfate and potassium per- sulfate; organic hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peroxydicarbonate esters such as diisopropyl peroxydicarbonate, peracetic acid and per- benzoic acid, sometimes activated by water-soluble reducing agents such as fenous compounds, sodium bisulfite or hydroxylamine hydrochloride, and other free radical producing materials such as 2,2'-azobisisobutyronitrile.
  • inorganic peroxides such as hydrogen peroxide and inorganic persul
  • a further additive which may be added to the mixture contents is a conventional chain transfer agent, such as an alkyl polyhalide or mercaptan.
  • chain transfer agents include bromoform, carbon tetrachloride, carbontetrabromide, bromoethane, C ⁇ -C
  • water-immiscible solvents may be used in the agricultural formulations of the present invention.
  • these water- immiscible solvents are the aromatic liquids, particularly alkyl substituted benzenes such as xylene or propyl benzene fractions, and mixed naphthalene and alkyl naphthalene fractions; mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene, polybutenes; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty acids such as the dimethyl amide of caprylic acid; chlorinated aliphatic and aromatic hydrocarbons such as 1,1, 1 -trichloroethane and chlorobenzene, esters of glycol derivatives, such as the acetate of the n-butyl, ethyl, or methyl ether of di ethylene glycol, the acetate
  • Pesticidal substances suitable for use in the composition in accordance with the invention include, for example, amitraz, bromophos, azinphos-ethyl, bromopropylate, azinphos-methyl, butocarboxin, *benzoximate, butoxycarboxin, bifenthrin, chlordimeform, binapacryl, chlorobenzilate, bioresmethrin, chloropropylate, chlo ⁇ yrifos, chlo ⁇ hoxim, chlo ⁇ yrifos-methyl, fenamiphos, cyanophos, fenobucarb, *cyfluthrin, gamma-HCH,
  • Ethiofencarb resmethrin, dinobuton, temephos, tetradifon, tetramethrin, tralomethrin, xylylcarb, N-2,3-dihydro-3-methyl-l,3-thiazol-2-ylidene-2,4- xylidine (wherein compounds denoted with a "*" conespond to l-[3,5-dichloro-4-(l,l,2,2-tetrafluoro ethoxy phenyl]-3-(2,6- difluorobenzoyl) urea), and mixtures thereof.
  • pesticidal materials include acylurea insecticides, organophosphorous insecticides, pyrethroid insecticides, aryloxyaryl herbicides and sulfonamide herbicides.
  • examples of such pesticides include the acylurea insecticides described in U.S. Pat. Nos. 4,148,902: 4,173,637 and Re.
  • chlo ⁇ yrifos and chlo ⁇ yrifos methyl the pyrethroid insecticides such as cypermethrin, permethrm and fenvalerate:the aryloxyaryl herbicides described in U.S. Pat. Nos.
  • Fungicidal substances suitable for use in the composition in accordance with the invention include, for example benalaxyl myclobutanil
  • Herbicidal substances suitable for use in the composition in accordance with the invention include, for example aclonifen chlo ⁇ ropham alachlor cycloxydim anilophos diclofop-methyl benfluralin diethatyl bensulide dimethachlor benzoylprop-ethyl dinitramine bifenox ethalfluralin bromoxynil ethofumesate butralin fenoxaprop ethyl flurochloridone flamprop-methyl fluchloralin phenisopham flumetralin phenmedipham fluorodifen profluralin fluoroglycofen ethyl propachlor flurecol butyl propanil fluoroxypyr ester pyridate haloxyfop-methyl *quizalafop-ethyl haloxyfop ethoxyethyl tridiphane monalide *trifluralin napropamide nitrofen ox
  • pesticides such as the nitrification inhibitor nitrapyrin may al be employed.
  • the pesticide may be an organosoluble derivative of a pesticidal compound which is itself poorly organosoluble or insoluble, such as cyhexatin dodecylbenzene sulphonate.
  • compositions of the invention may also include optional adjuvants such as freezing point depressants preferably in amounts of 0-15%, flow aids to prevent caking or aid in the redispersion of bottom sediment preferably in amounts of 0-5%, thickening agents preferably amounts of 0-3% and defoamers preferably 0-1% to improve the overall properties under field storage and use conditions.
  • optional adjuvants such as freezing point depressants preferably in amounts of 0-15%, flow aids to prevent caking or aid in the redispersion of bottom sediment preferably in amounts of 0-5%, thickening agents preferably amounts of 0-3% and defoamers preferably 0-1% to improve the overall properties under field storage and use conditions.
  • compositions may be inco ⁇ orated into the compositions to maintain or improve biological efficacy of the composition.
  • surfactants for increasing penetration of the active substances or salts may be inco ⁇ orated into the compositions to maintain or improve biological efficacy of the composition. These may be inco ⁇ orated into the oil phase or aqueous phase as appropriate. All documents, e.g., patents and journal articles, cited above or below are hereby inco ⁇ orated by reference in their entirety.
  • the amount of agglomerated polymers, or "coagulum", in the resulting lattices at the conclusion of the polymerization is determined by collecting the agglomerated polymers using a 20 mesh screen that has openings sufficiently large enough to allow the discrete un- agglomerated polymers to pass, rinsing the collected agglomerated polymers with water, and weighting the remaining agglomerated polymers trapped on the screen.
  • the percent coagulum is calculated by dividing the weight of the coagulum by the theoretical weight of the entire latex based upon the weights of the ingredients used for the polymerization reaction.
  • the viscosity of the resulting lattices following polymerization is determined by using a RV Brookfield synchro-lechtric viscometer equipped with a No. 3 spindle. During such determinations 950 ml of each latex is placed in a 1000 ml beaker and the viscometer
  • the mechanical stability of the lattices following exposure to mechanical stress is evaluated to determine the extent to which there is a change in the viscosity and/or the visual presence of coagulum. More specifically, two cups of each latex are placed in a five-cup stainless steel Hamilton Beach blender, and the blender operated at medium speed until the latex coagulates. Failure of the latex is the point at which coagulum separation can be visually observed; a longer time of blending at medium speed without coagulum separation, i.e. a longer time before failure, is a highly desirable characteristic of a latex.
  • Solids of lattices were determined by concentrating the latex at 120°C in an oven to
  • the particle size of the resulting lattices is determined with a NICOMP 370C Auto- dilution particle size analyzer using standard methods and procedures for operation of such equipment and such data recorded for 50% volume in units of nano-meters.
  • the water sensitivity, e.g. hydrophobicity, of the resulting lattices was determined by ASTM D724-45.
  • the allylamine and propyl amine may be obtained from Aldrich Chemical Company (USA).
  • MMA/BA/MMA methylmethacrylate/butylacrylate/methacrylic acid
  • ADDBS dodecylbenzenesulfonic acid
  • the temperature of the reactor contents is adjusted to about 77-79°C, and about 75 g of the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 16.9 g of a solution of ammonium persulfate (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 82.5 g of water) is added to the reactor over a period of about 7 minutes with
  • the reactor temperature is
  • a methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA MMA) co-polymer (in a weight ratio of about 48:49:3), in combination with the propylamine salt of dodecylbenzenesulfonic acid (PDDBS), is prepared as follows. About 330 g of deionized water and about 25 g of PDDBS (as a 20% active aqueous solution) are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor is purged with nitrogen (99% pure), and heated to
  • the temperature of the reactor contents is adjusted to about 77-79°C, and
  • a methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer (in a weight ratio of about 46.1:50.8:3.1) in combination with the allylamine salt of nonyl phenol 9-EO phosphate acid ester (Cedephos CP-610) is prepared as follows. About 249 g of deionized water and about 11.0 g of the allyl amine salt of Cedephos CP-610 (as a 20% active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor
  • reactor contents is adjusted to about 71-74°C, and about 74 g of the monomer mixture (20% of a total of 371 g of the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor.
  • 15 g of a solution of ammonium persulfate (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 74.0 g of water) is added to the reactor over a period of about 10 minutes with continued agitation, during which time there is an
  • the reactor temperature of about 78-81°C.
  • the reactor temperature is then elevated to about 82-84°C with continued agitation, for about 15 minutes. After this 15 minute period, the reactor is
  • Example 4 (Comparative Example :
  • a methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer (in a weight ratio of about 46:51:3), in combination with the propylamine salt of nonyl phenol 9-EO phosphate acid ester (Cedephos CP-610) is prepared as follows. About 251 g of deionized water and about 10.2 g of propylamine salt of Cedephos CP-610 (as a 20% active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor is purged with
  • the reactor temperature is then elevated to about 82-84°C with continued agitation, for about
  • Latex product is completely removed from the reactor and gravity filtered using a first 20 mesh screen and then a second 250 mesh screen.
  • the total latex coagulum (i.e. solids) from both mesh screens is collected, combined and weighed.
  • Various physiochemical properties of the latex are reported in Table II.
  • a methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer (in a weight ratio of about (48:49:3), in combination with the allylamine salt of lauric acid (ALA) is prepared as follows. About 205 g of deionized water and about 1.6 g of ALA (as a 20%) active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor
  • reactor contents is adjusted to about 71-73°C, and about 75 g of the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor.
  • 15 g of a solution of ammonium persulfate (20% of the total solution of 1.8 g of ammonium persulfate dissolved in 75.0 g of water) is added to the reactor over a period of about 10 minutes with continued agitation, during which time there is an
  • temperature is then elevated to about 83-85°C with continued agitation, for about 15 minutes.
  • a methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer (in a weight ratio of about (48:49:3), in combination with the propylamine salt of lauric acid (PLA) is prepared as follows. About 206 g of deionized water and about 1.6 g of PLA (as a 20% active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor
  • reactor contents is adjusted to about 71-73°C, and about 7 g of the monomer mixture (2%> of a
  • temperature is then elevated to about 83-85°C with continued agitation, for about 15 minutes.
  • Example 7 A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio of about 78.9:21.1), in combination with the allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared as follows. About 245 g of deionized water and about 1.5 g of ADDBS (as a 20% active aqueous solution), 1.5 g of PDDBS (as a 23 % active aqueous solution), and 1.0 g of sodium sulfate are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor is purged with nitrogen (99% pure), and heated
  • the temperature of the reactor contents is adjusted to about 63-65°C, and
  • the temperature of the reaction contents is adjusted to about 76-78°C and about 294g of the BA/VA monomer mixture (the remaining 80 %>), 61.5 g of the ammonium persulfate solution (the remaining 80%), 27.46 g ADDBS (as a 20% active aqueous solution), and 8.59 g PDDBS (as a 23 % active aqueous solution) are simultaneously charged to the reactor over a period of 4 hours with continued agitation, while
  • the reactor temperature is
  • Example 8 (Comparative Example): A vinylacetate/butyl acrylate (VA BA) co-polymer (in a weight ratio of about
  • PDDBS dodecylbenzenesulfonic acid
  • the reactor is purged with nitrogen (99% pure), and heated to about 65-68°C.
  • reaction contents is adjusted to about 76-78°C and about 240 g of the BA/VA monomer mixture (the remaining 80 %>), 40.7 g of the ammonium persulfate solution (the remaining 80%), 16.8 g PDDBS (as a 23% active aqueous solution) are simultaneously charged to the reactor over a period of 4 hours with continued agitation, while keeping the
  • reactor contents at a temperature of about 78-80°C.
  • the reactor temperature is then elevated
  • the reactor is cooled to about 30°C.
  • the resulting latex product is completely removed from the reactor and gravity filtered using a first 20 mesh screen and then a second 250 mesh screen.
  • the total latex coagulum (i.e. solids) from both mesh screens is collected, combined and weighed.
  • Various physiochemical properties of the latex are reported in Table III.
  • a vinylacetate/butyl acrylate (VA/BA) co-polymer in a weight ratio of about 78.9:21.1, in combination with the allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and the ammonium salt of lauryl ether sulphate with 30 EO groups (ALSE) is prepared as follows. About 245 g of deionized water and about 1.5 g of ADDBS (as a 19%> active aqueous solution) and 1.0 g of sodium sulfate are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means.
  • ADDBS dodecylbenzenesulfonic acid
  • ALAE ammonium salt of lauryl ether sulphate with 30 EO groups
  • the reactor is purged with nitrogen (99% pure), and heated to about 65-68°C.
  • the temperature of the reaction contents is adjusted to about 78-81°C and about 294g of the BA/VA monomer mixture (the remaining 80 %), 61.4 g of the ammonium persulfate solution (the remaining 80%), 27.8 g ADDBS (as a 20% active aqueous solution), and 6.3 g ALSE (as a 30 % active aqueous solution) are simultaneously charged to the reactor over a period of 4 hours with continued agitation, while keeping the reactor contents at a temperature of about 78-82°C. The reactor temperature is then elevated to about 82-84°C
  • a vinylacetate/butyl acrylate (VA/BA) co-polymer in a weight ratio of about 78.9:21.1 ), in combination with the allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared, using redox couple as initiators, as follows.
  • the temperature of the reaction contents is adjusted to about 68-72°C, and 54.9 g of the sodium metabisulphite solution (the remaining 80%), 54.8 g of the ammonium persulfate solution (the remaining 80%), 503 g of the BA/VA monomer mixture (the remaining 98 %), 29.3 g of ADDBS (as a 19 % active aqueous solution), and 10.3 g of PDDBS (as a 23 % active aqueous solution) are simultaneously added over a period of three hours with continued agitation, while keeping the reactor contents at a temperature of about
  • the reactor temperature is then elevated to about 75 - 78°C with continued agitation, for about 15 minutes. After this 15 minute period, the reactor is cooled to about
  • a methylmethacrylate/butylacrylate/methacrylic acid (M lA/BA/MMA) co-polymer (in a weight ratio of about 48:49:3), in combination with the allylamine salt of laureth-3EO- sulfate (AES-3), is prepared as follows. About 205 g of deionized water and about 1.6 g of
  • AAES-3 (as a 25.5% active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means.
  • the reactor is purged with nitrogen (99% pure), and heated to about 77 - 79°C.
  • the reactor is cooled to about 30°C.
  • the resulting latex product is completely removed from
  • the total latex coagulum (i.e. solids) from both mesh screens is collected, combined and weighed.
  • the resulting latex has the following charateristics: Solids 48.41%
  • Example 12 A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer (in a weight ratio of about 48:49:3), in combination with the allylamine salt of lauryl sulfate (AS), is prepared as follows. About 222 g of deionized water and about 2.3 g of AS (as a 17.2% active aqueous solution), are placed in a reactor suitable for emulsion polymerization, equipped with agitation means, heating means and cooling means. With agitation, the reactor
  • the reactor temperature is then elevated to about 82 - 84°C with continued agitation,
  • the resulting latex product is completely removed from the reactor and gravity filtered using a first 420 mesh screen and then a second 250 mesh screen.
  • the total latex coagulum (i.e. solids) from both mesh screens is collected, combined and weighed.
  • the resulting latex has the following charateristics:
  • Coagulum 0.36g ( ⁇ 0.05% on total batch weight)
  • the hydrophobicity of a latex prepared using a typical non-polymerizable surfactant was compared to that of a latex prepared using a representative polymerizable surfactant of the present invention. It has been discovered that the latex prepared in Example 1 (using ADDBS) possess remarkable hydrophobicity, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS). [Need to insert ASTM method and description here.] The change in contact angle as a function of time for a water droplet at each of the latex film surfaces was measured; the results are shown below.
  • a rapidly increasing contact angle as observed from a latex film indicates that the water droplet is penetrating the film due to surfactant related imperfections of the film.
  • a constant water droplet contact angle indicates the desirable result whereby water is unable to penetrate the hydrophobic film.
  • the hydrophobicity of a latex prepared using a typical non-polymerizable surfactant was compared to that of a latex prepared using a representative polymerizable surfactant of the present invention, whereby the different latex films were coated and heat cured onto porous filter paper and treated with water.
  • water undesirably, readily penetrated through the film and absorbed into the paper in a few seconds for the latex derived from the AmDDBS surfactant.
  • the latex film derived from the ADDBS surfactant did not allow the water to penetrate or absorb; the water droplet maintained its original shape on the latex film, prior to being influenced by evaporation effects (at least thirty minutes).
  • adhesion properties of a latex prepared using a typical non-polymerizable surfactant were compared to that of a latex prepared using a representative polymerizable surfactant of the present invention. It has been discovered that the latex prepared in Example 1 (using ADDBS) possess a vastly superior adhesion profile, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS). Adhesion data were collect for each latex acrylic lattice using ASTM method D897. This test method is a standard test for adhesion called "block pull"; results from the test are indicated in pounds per square inch (p.s.i.), wherein the higher the p.s.i.
  • Adhesive failure is defined as the point at which the latex, upon application of a pulling force, no longer adheres to the surface of the substrate.
  • Cohesive failure is defined as the point at which the latex itself fails, i.e. where the latex splits into two or more portions, but remains bound to the substrate.
  • the adhesion tests were conducted using an Instron Model 1123, with a 5000 pound load cell, a sample size of 0.5 g of latex, a surface area of 4 in , whereby the treated sample blocks were allowed to dry at room
  • Latex Surfactant Adhesive Failure p.s.i AmDDBS (non-polymerizable) 65
  • Latex film yellowing properties of a latex prepared using a typical non- polymerizable surfactant were compared to that of a latex prepared using a representative polymerizable surfactant of the present invention. It has been discovered that the latex prepared in Example 1 (using ADDBS) possess a greatly improved film yellowing profile, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS). Latex film yellowing was compared after aging the films six months at room temperature, at approximately standard atmospheric conditions. It is highly desirable, as known by one skilled in the art, to produce a latex film which does not yellow upon application to a surface, with the passage of time.
  • the ADDBS-derived latex was plainly observed to be significantly lighter color than the AmDDBS-derived latex.
  • Absorbence measurements were taken for each latex at 350 ran and 420 ran; the lower the absorbance at a given wave length, the lighter the latex (i.e. the less yellow the latex). Results of the measurements for the two latexes are shown below.
  • Example 1 (using ADDBS) possess improved scrubability characteristics, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid,
  • Latex Surfactant Latex FTIR Absorbance (x 10 "4 )
  • the oil phase i.e. agricultural technical + optional supplemental surface active agent; i.e. co-surfactant, and optional water immissible solvent
  • the oil phase may contain from 10 to 80% w/v of the agricultural technical, preferably 10 to 60% and most preferably 20 to 50% w/v.
  • the latex content of the composition will depend upon the latex type as well as the pesticide and surfactant type but may vary from 5% w/v to 80% w/v, preferably 5 to 60% w/v and most preferably 10 to 50% w/v.
  • the amount of the latex to be employed in the compositions in the present invention should be as low as possible, provided that it is sufficient to stabilize the emulsion. Not only is the use of excess polymer latex generally uneconomical, it also means that the resulting composition is unable to carry such a high loading of active ingredient, which makes the resulting compositions unattractive to the purchaser.
  • a variety of stirring methods may be employed, from simple shaking, stirring through to sonication and high shear emulsification, including bead milling.
  • the aqueous dispersions in accordance with at least the prefened embodiments of the invention are useful for the control of a wide variety of target organisms, being advantageously employed wherever a conventional emulsifiable concentrate finds use, but having the advantages of being water based and therefore of low flammability, lower dermal toxicity in many cases, ability to be packed in HDPE and being at least as efficacious as an emulsifiable concentrate counterpart.
  • NMS non-migrating surfactnat: polymerizable surface active agent- derived
  • Formulations of NMS show superior physical stability compared to migrating latexes.
  • Acetochlor latex formulations were prepared by adding 12.5 g of acetochlor technical and 1.39 g of Makon 10 (optional co-surfactant) to 25 g of either a migrating latex prepared according to Latex Example #1, using lauryl alcohol 3-mole ethylene oxide, ether sulfate allyl amine salt (a NMS latex; also called AU-7 latex) and Latex Example #2, using lauryl alcohol 3-mole ethylene oxide, ether sulfate sodium salt (a traditional surfactant latex; also called B-330A latex).
  • Formulations of traditional migrating (Latex Example #2, using lauryl alcohol 3-mole ethylene oxide, ether sulfate sodium salt) and NMS latexes (Latexes prepared according to
  • Latex Example #1 also called AU-1 latex
  • Latex Example #3 also called AU-9 latex
  • chlo ⁇ yrifos as the active ingredient were prepared by the previously described technique.
  • the chlorpyrifos was dissolved in Aromatic 150 solvent plus 10% w/w Makon 10.
  • the concentration of chlo ⁇ yrifos in the solvent plus co-surfactant solution was 65% w/w.
  • Each formulaton contained 25 g of the latex, 15 g. of chlo ⁇ yrifos solution, and 10 g of DI water.
  • the formulations were then stored in 2 oz glass bottles with nylene caps, at 50C for 60 days.
  • the higher concentration products also su ⁇ risingly have much more rapid dispersion properties when diluted compared to high concentration traditional latex pesticide formulations.
  • the formulations were made by blending acetochlor technical with 10% (relative to the acetochlor) Makon 10 and mixing until uniform. To a beaker was added 12.5 g. of latex (migrating or non-migrating), and 5 g of DI water. The latex and water were stined with a magnetic stir bar until uniform, then the acetochlor solution was added to the latex until the viscosity was too high to permit agitation.
  • Oil phase weight added 21.35 g 26.95 g
  • the dispersions show only a trace of creamy separation after 1 hour at room
  • NMS latexes show superior dilution stability compared to tradional type latexes.
  • Samples of a migrating type latex B-330A , and a non-migrating type latex AU-7 were each diluted 1:50, 1:100, 1:1000 in 100 mL conical centrifuge tubes. The dilutions were made in WHO 342 ppm test water, and the separation was noted after 10 days. All of the B-330A samples showed traces of separation at the bottom of the tubes, whereas the AU-7 samples showed no separation.
  • a formulation was prepared to contain propanil, by adding 20 g of a 36% ai stock solution, containing 1.5 g of Makon 10 as co-surfactant, to 20 g of AU-9 latex containing 10 g of additional DI water. The oil phase was added to the latex and water solution gradually while the mixture was being stined with a magnetic stir bar. The formulation formed was uniform, and physically stable, showing no separation after 3 months.
  • Example 6 Stable formulations of trifluralin and metolachlor were prepared using AU-7 latex, by blending oil phase into water plus latex and stirring until a uniform mixture was achieved.
  • the oil phase was mixed with Makon 10 as co-surfactant prior to adding the oil to the latex.
  • the trifluralin was dissolved in Aromatic 150 solvent to form a 45% AI stock solution on a weight/weight basis.
  • the metolachlor technical was used as-is with no dilution.
  • compositions are below:
  • NMS latex formulations show excellent dilution stability.
  • Formulations that had been prepared previously were diluted 5 mL of formulation to 95 mL of 342 ppm WHO test water, and mixed in a 100 mL stoppered mixing cylinder. After the dispersions were formed, the cylinders were stored in a rack at room temperature for 14 days. At the end of 14 days, the amount of separation was recorded. The data are below:
  • NMS latex formulations show exellent dilution stability when diluted below 1:50.
  • Formulations were prepared with two non-migrating latexes for each of three pesticide active ingredients.
  • the latexe (either AU-1 or AU-9) formulations and were diluted 1:200 in 50 mL mixing cylinders containing 1000 ppm (as CaCO3) testwater. After 5 days, the separation was measured.
  • the basic formulation is below, as is the composition of all stock solutions and the separation data.
  • Chlo ⁇ yrifos stock solution contained 67% technical, 23% Aromatic 150, 10% Makon 10.
  • Metolachlor stock solution contained 90% technical, 10% Makon 10.
  • Acetochlor stock solution contained 90% technical, 10% Makon 10.
  • the formulations were made by adding the water phase and latex to a 2 oz vial, then the oil phase was added. The vials were immediately mixed using a vortex mixer. Dilution stability results after 5 days, 1:200 in 1000 ppm test water:
  • Metolachlor AU-1 None Metolachlor AU-9 Slight trace
  • NMS latexes show excellent stability at dilutions below 1 :200.
  • Chlo ⁇ yrifos formulations were prepared by blending a chlo ⁇ yrifos stock solution containing 67% pesticide technical, 10% Makon 10 and 23% Aromatic 150 solvent, with an AU-1 or AU-9 latex and water. The formulations contained 30% stock solution, 20% DI water and 50% latex. Both formulations were then diluted serially from l%o down to 0.001% in tap water, and then the separation was measured after 3 hours. The results are below: Dilution AU-1 Latex AU-9 Latex
  • Example 10 NMS latex pesticide formulations show excellent stability under shear conditions.
  • a metolachlor NMS latex formulation was prepared and compared with an EC formulation of the same active ingredient for dispersion stability under shear conditions similar to those expected under normal agricultural sprayer conditions. Both formulations were diluted to a use rate of 3.6 g. active ingredient per liter of spray solution, in a 2 liter laboratory spray apparatus.
  • the test emulsions / dispersions were recirculated through a centrifugal pump system at 20 psi initial pressure. Every 10 minutes a 100 mL aliquot was removed through a Teejet SS8003 nozzle.
  • the test was run for 60 minutes for each formulation, and readings from the pressure guage (indicating the in-line 100 mesh strainer was being clogged) were recorded. 30 minutes after each aliquot was removed, the separation in the 100 mL cylinder was measured. Equal separation over time and no significant increase in the pressure reading over time indicates a stable system. The results for both types of formulations are below.
  • the test was run in 342 WHO water.
  • Example 11 NMS latex formulations show excellent physical stability.
  • An acetochlor formulation was prepared by blending 25 g of AU-9 latex (2157-24) with 10 g of DI water then adding 15 g of a 90/10 solution of acetochlor/Makon 10. The mixture was blended with a magnetic stir plate apparatus until uniform. 2.5 mL of the sample was dispersed in 47.5 mL of 342 ppm WHO water in a mixing cylinder. The mixing cylinder was inverted 10 times and then the separation was recorded at 3 hours. The remainder of the sample was stored at 50C for 60 days. At 30 and 60 days, the sample was removed from the oven and allowed to equilibrate to room temperature.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé amélioré de fabrication de préparations agricoles et de polymères latex selon lequel on utilise au moins un monomère éthyléniquement insaturé, au moins un agent de surface actif polymérisable et au moins un agent technique. L'agent de surface actif polymérisable est capable de se copolymériser avec des monomères traditionnels utilisés pour former des latex. Il est, de préférence, entièrement consommé en cours de polymérisation. Les polymères latex de la présente invention conviennent bien à la fabrication de préparations agricoles qui contiennent un pesticide ou un herbicide. Combinés à de divers pesticides et herbicides, les polymères fabriqués selon le procédé de l'invention conviennent bien à la protection des cultures.
PCT/US1999/017029 1998-07-28 1999-07-28 Latex polymeres prepares a partir de sels amines ethyleniquement insatures WO2000005950A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99935970A EP1100325A1 (fr) 1998-07-28 1999-07-28 Latex polymeres prepares a partir de sels amines ethyleniquement insatures
BR9912572-2A BR9912572A (pt) 1998-07-28 1999-07-28 Formulação agrìcola
AU51333/99A AU5133399A (en) 1998-07-28 1999-07-28 Polymer latexes prepared from ethylenically unsaturated amine salts
CA002338708A CA2338708A1 (fr) 1998-07-28 1999-07-28 Latex polymeres prepares a partir de sels amines ethyleniquement insatures

Applications Claiming Priority (2)

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US9442398P 1998-07-28 1998-07-28
US60/094,423 1998-07-28

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10148570A1 (de) * 2001-10-01 2003-04-10 Goldschmidt Ag Th Mikroorganismen und eine Wasser-in-Öl-Polymerdispersion enthaltende Zusammensetzung und deren Verwendung
US7774978B2 (en) 2001-03-21 2010-08-17 Stepan Company Method of controlling the release of agricultural active ingredients from treated plant seeds
CN114015185A (zh) * 2021-10-20 2022-02-08 界首市天鸿新材料股份有限公司 一种可生物降解性热收缩膜及其加工工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7363978B2 (en) 2005-05-20 2008-04-29 Halliburton Energy Services, Inc. Methods of using reactive surfactants in subterranean operations

Citations (5)

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WO1989003175A1 (fr) * 1987-10-14 1989-04-20 Dow Chemical Company Limited Compositions a usage agricole contenant du late
EP0374796A2 (fr) * 1988-12-19 1990-06-27 Dowelanco Formulations d'émulsions stables de pesticides organiques insolubles dans l'eau
US5478883A (en) * 1995-04-11 1995-12-26 Basf Corporation Emulsion polymerization process utilizing a specifically defined ethylenically unsaturated polymerizable water-soluble nonionic surfactant formed by the reaction of a diallylamine, ethylene oxide and propylene oxide and/or butylene oxide
WO1998032726A1 (fr) * 1997-01-28 1998-07-30 Stepan Company Nouveaux sels amines insatures en ethylene, d'acides sulfoniques, phosphoriques et carboxyliques
WO1998032773A1 (fr) * 1997-01-28 1998-07-30 Stepan Company Procede perfectionne de polymerisation en emulsion utilisant des sels amines non satures ethyleniquement d'acides sulfoniques, phosphoriques et carboxyliques

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WO1989003175A1 (fr) * 1987-10-14 1989-04-20 Dow Chemical Company Limited Compositions a usage agricole contenant du late
EP0381691B1 (fr) * 1987-10-14 1992-10-07 Dowelanco Composes agricoles a base de latex
US5321049A (en) * 1987-10-14 1994-06-14 Dowelanco Agricultural compositions containing latexes
EP0374796A2 (fr) * 1988-12-19 1990-06-27 Dowelanco Formulations d'émulsions stables de pesticides organiques insolubles dans l'eau
US5478883A (en) * 1995-04-11 1995-12-26 Basf Corporation Emulsion polymerization process utilizing a specifically defined ethylenically unsaturated polymerizable water-soluble nonionic surfactant formed by the reaction of a diallylamine, ethylene oxide and propylene oxide and/or butylene oxide
EP0737693A1 (fr) * 1995-04-11 1996-10-16 Basf Aktiengesellschaft Procédé de polymérisation en émulsion utilisant un émulsifiant nonionique soluble dans l'eau insaturé éthyléniquement polymérisable, préparé par réaction d'un diallylamine et l'oxyde d'éthylène et l'oxyde de propylène et/ou l'oxyde de butylène
WO1998032726A1 (fr) * 1997-01-28 1998-07-30 Stepan Company Nouveaux sels amines insatures en ethylene, d'acides sulfoniques, phosphoriques et carboxyliques
WO1998032773A1 (fr) * 1997-01-28 1998-07-30 Stepan Company Procede perfectionne de polymerisation en emulsion utilisant des sels amines non satures ethyleniquement d'acides sulfoniques, phosphoriques et carboxyliques

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7774978B2 (en) 2001-03-21 2010-08-17 Stepan Company Method of controlling the release of agricultural active ingredients from treated plant seeds
DE10148570A1 (de) * 2001-10-01 2003-04-10 Goldschmidt Ag Th Mikroorganismen und eine Wasser-in-Öl-Polymerdispersion enthaltende Zusammensetzung und deren Verwendung
CN114015185A (zh) * 2021-10-20 2022-02-08 界首市天鸿新材料股份有限公司 一种可生物降解性热收缩膜及其加工工艺
CN114015185B (zh) * 2021-10-20 2024-01-12 界首市天鸿新材料股份有限公司 一种可生物降解性热收缩膜及其加工工艺

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