EP1100325A1

EP1100325A1 - Polymer latexes prepared from ethylenically unsaturated amine salts

Info

Publication number: EP1100325A1
Application number: EP99935970A
Authority: EP
Inventors: Alfred K. Schultz; Adnan Siddiqui; Brett Butler
Original assignee: Stepan Co
Current assignee: Stepan Co
Priority date: 1998-07-28
Filing date: 1999-07-28
Publication date: 2001-05-23
Also published as: WO2000005950A1; BR9912572A; CA2338708A1; AU5133399A

Abstract

An improved method of making agricultural formulations and latex polymers is provided, wherein the method utilizes at least one ethylenically unsaturated monomer, at least one polymerizable surface active agent and at least one technical. The polymerizable surface active agent is capable of co-polymerization with traditional monomers used to form latexes and is preferably substantially completely consumed during the course of the polymerization. The latex polymers of the instant invention are well suited for use in preparing agricultural formulations which contain a pesticide or a herbicide. Polymers produced by the method of the present invention, in combination with a variety of pesticides and herbicides, are well suited for use in agricultural crop protection.

Description

POLYMER LATEXES PREPARED FROM ETHYLENICALLY UNSATURATED AMINE SALTS

BACKGROUND OF THE INVENTION

Field of the Invention:

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.

Description of the Related Art

The 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. During a typical emulsion polymerization, a surfactant is used to suspend small portions of monomer in a continuous or semi-continuous aqueous phase. Typically, 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. In a traditional emulsion polymerization reaction, 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.

Several proposals have been made in the prior art to employ a polymerizable surfactant as the surface active agent during an emulsion polymerization reaction. U.S. Pat. No. 5,478,883 (incorporated herein by reference in its entirety) describes the use of ethylenically unsaturated polymerizable water-soluble nonionic surfactants formed by the reaction of a diallylamine compound with ethylene oxide, propylene oxide or butylene oxide, in emulsion polymerization reactions. Similarly, U.S. Pat. No. 5,162,475 (incorporated herein by reference) provides alpha-beta ethylenically unsaturated poly(alkylenoxy) polymerizable surface active compounds for use in emulsion polymerization. For additional examples of polymerizable surfactants for use in emulsion polymerization processes, see U.S. Pat. Nos. 4,377,185 and 4,049,608.

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.

Also, particularly with respect to agricultural formulations, see for example, 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 chloφyrifos or chloφyrifos-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. a pesticide) dissolved in a water-miscible solvent or the particles of the latex. 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 incoφorating one pesticide in a dispersed latex phase and the other ingredient within the continuous aqueous phase. U.S. Pat. No. 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. U.S. Pat. No. 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.

It is generally desired of such pesticidal compositions that they should be easy to handle, and easy to apply in any desired concentration. For this reason, herbicidal compositions are generally supplied in the form of wettable powders, emulsifiable concentrates and the like. In the formulation of emulsifiable concentrates, it is generally necessary to incoφorate substantial quantities of organic solvents, and this can result in substantial problems of dermal toxicity and flammability. Furthermore, 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. In addition, the incoφoration of high levels of organic solvents in emulsifiable concentrates gives rise to problems of phytotoxicity to crops when the pesticidal substances are utilized. Much of the related are requires the use of heat to incoφorate the agricultural technical in to the polymer latex, i.e. to make the mixture a single phase mixture. Heat is generally necessary to drive the incoφoration of the technical actives into the polymer latex. Additionally, these disclosures describe agricultural formulations which may phase separate upon extended storage. Many of these formulations have the distinct disadvantage of requiring the use of water-miscible solvents to help transport the oil phase through the aqueous phase and into the latex particles. Typically, the use of such solvents requires subsequent removal of the solvent when preparing a finished agricultural formulation. Such removes is costly, time consuming and presents a disposal concern. Several of the suggested methods above have the draw-back of requiring the use of co-solvents, such as methyl laurate, to aid in the absoφtion of agricultural active ingredients into the latex polymer particles.

Additionally, the above approaches often may not allow for dilution stability. Several of the above approaches are oil in water emulsions which must be prepared under high shear prior to blending with the latex. Thus there exists a need for stable, easy to prepare agricultural latex -based formulations which overcome or decrease the afforementioned difficulties. Agricultural latex-based formulations which are solvent/co-solvent free and do not require the use of excessive heat to prepare, i.e. drive the actives into the latex, are highly desireable. Additionally, these formulations would desireabally would not contain water-miscible solvents to help transport the oil phase through the aqueous phase and into the latex particles. It is highly desirable to develop a latex -based agricultural formulation which does not require the formation of an oil in water emulsion prior to mixing with the polymer latex. A need exists in the art for agricultural latex-based formulations which high dilution stability are also highly desirable. SUMARY OF THE INVENTION

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. As known by one skilled in the art, upon mixing the acid and nitrogenous base together, the nitrogenous base becomes a conjugate acid and the acid becomes a conjugate base. Accordingly, an improved method is provided 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. Generally, 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. Somewhat preferably, the nitrogen atom is linked covalently, directly or indirectly, to the ethylenically unsaturated moiety of the nitrogenous base. Also preferably, the polymerizable surface active agent is in the form of an amine salt, rather than a quaternary nitrogen compound. Additionally, although somewhat less preferred, 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. As used herein, the terms pesticide (or pesticidal) and insecticide (or insecticidal) are interchangable.

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 incoφorated into it, surface active agent monomers and/or homopolymeric surface active agents. The various final 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.

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. However, while not usually desirable, low molecular weight volatile organic compounds and/or residual formaldehyde may be present in the polymerization products of the present invention. Further, 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

(i.e. all at once), a continuous mode (i.e. by addition of an amount of the polymerizable surface active agent throughout the polymerization) or in 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. 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. As known by one skilled in the art, upon mixing the acid and nitrogenous base together, 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.

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. Although not critical to the present invention, 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. Conversely, 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.

In accordance with a first aspect of the present invention, there is provided 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.

The term "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. The term "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 (wateπcomposition) 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.

These and other objects and advantages, as well as the scope, nature, and utilization of the claimed invention will become apparent to those skilled in the art from the following detailed description and claims.

DETAILED DESCRIPTION OF THE INVENTION

A method is provided for forming agricultural formulations using latex polymers prepared from monomers and polymerizable surface active agents, wherein the method 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. Generally, 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. In general, the polymerization process of

the present invention will be carried out from about 20°C to about 120°C (e.g., between about

50°C and about 1 10°C). These polymerization temperatures will vary with respect to the

reactivity and concentration of the polymerization initiator being used. Batch polymerization times may vary depending on the method of polymerization and the monomers being polymerized. Such times may vary from about 10 minutes to about 10 hours. In general, the mixture may be a solution, emulsion, suspension or dispersion of the ethylenically unsaturated monomer and the polymerizable surface active agent. Further, the polymerizable surface active agent may be provided to the mixture as an aqueous solution. Additionally, although somewhat less preferred, the agricultural technical may be added before or during the polymerization.

In accordance with the present invention, 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). Accordingly, 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. In a somewhat prefened embodiment, 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. In a more prefened embodiment, 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. In a most prefened embodiment, the polymerizable, surface active agent is substantially completely (i.e. greater than 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 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. In a prefened embodiment, 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. In a more prefened embodiment, 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. In another embodiment, 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. In general, 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. However, in a somewhat less prefened embodiment, 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. 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.

In another embodiment, 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. In accordance with this embodiment, 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. In one alternative, 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). Without being bound by any particular theory, it is believed that the nitrogenous base is incoφorated into the polymer back-bone and the acid forms an ion pair, i.e. a salt, with the nitrogen atom of the nitrogenous base, thereby adhering to the polymer and forming a positively charged nitrogen atom. In another alternative within the purview of this embodiment, 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. In another alternative, 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. In another embodiment, 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. Optionally, 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. In another embodiment, 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 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. In another embodiment, 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 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; and wherein the supplemental surface active agent is generally non-polymerizable and is defined herein.

In another embodiment, 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 least one nitrogen atom and at least one ethylenically unsaturated moiety.

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

The 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. Examples of suitable ethylenically unsaturated monomers are, for example, mono- and polyunsaturated hydrocarbon monomers, vinyl esters (e.g., vinyl esters of C| to C₆ saturated monocarboxylic acids), vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and there alkyl esters (e.g., acrylic acid esters and methacrylic acid esters, particularly the Ci to Cι₂ alkyl, and more particularly the Ci to C₄ alkyl esters), the nitriles, vinyl and vinylidene halides, and amides of unsaturated carboxylic acids and amino monomers.

Examples of 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). Examples of vinyl and vinylidene halides include vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.

Examples of acrylic esters and methacrylic esters suitable for use in the present invention include Cι-Cι₂ (e.g., C]-C₄) 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. Typically 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.

Polymerizable Surface Active Agents 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. In a prefened embodiment of the present invention, 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. In general, although not required, 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. Although not critical to the present invention, 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. Additionally, 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. Conversely, 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, alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids, vinyl phosphinic

acids, phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters, α-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

(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.

Other 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, α-sulfonated alkyl ester acids, α-sulfonated ester

diacids, alkoxylated α-sulfonated alkyl ester acids, α-sulfonated dialkyl diester acids, di-α-

sulfonated dialkyl diester acids, α-sulfonated alkyl acetate acids, primary and secondary 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 alkylated cycloalkyl sulfuric acid esters, dendritic polysulfonic acids, dendritic polycarboxylic acids, dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, and tauric acids, and mixtures thereof.

Additionally in accordance with the present invention, suitable acids of the present invention include fluorinated carboxylic acids, fluorinated sulfonic acids, fluorinated sulfate acids, fluorinated phosphonic and phosphinic acids, and mixtures thereof. Due to their inherent hydrolytic instability, the sulfuric acid esters are preferably immediately converted to ethylenically unsaturated amine salts. For example, linear dodecyl alcohol is sulfated with SO₃ 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.

Scheme I: Formation of Dodecyl Sulfate Ethylenically Unsaturated Amine Salt

CH₃(CH₂) , i OH + SO₃ -» [CH₃(CH₂) , , OSO₃H] + H₂NCH₂CH=CH₂ -» [CH₃(CH₂), |OSO₃]^'[NH₃CH₂CH=CH₂]⁺

Additionally, for example, methyl laurate is sulfonated with SO to produce an

intermediate α-sulfonated lauryl methyl ester acid, as shown in Scheme II below. This acid is

neutralized with an ethylenically unsaturated nitrogenous base, such as allyl amine, to

produce an α-sulfonated lauryl methyl ester ethylenically unsaturated amine salt.

Additionally, an α-sulfonated lauryl methyl ester ethylenically unsaturated amine di-salt may

be produced as shown below in Scheme III. The α-sulfonated lauryl methyl ester

ethylenically unsaturated amine salt and the α-sulfonated lauryl fatty acid ethylenically

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.

Scheme II: Formation of α-Sulfonated Lauryl Methyl Ester Ethylenically Unsaturated Amine Salt

Scheme III: Formation of α-Sulfonated Lauryl Methyl Ester Ethylenically Unsaturated Amine Pi-Salt

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.

Scheme IV: Formation of a Sulfosuccinate Ester Ethylenically Unsaturated Amine Salt

NaHSO

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. Optionally, and somewhat less preferably, 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.

Scheme V: Formation Of A Fatty Sarcosinate Acid Ethylenically Unsaturated Amine Salt

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. Optionally, isethionic acid, or its sodium salt, may be combined with the ethylenically unsaturated nitrogenous base, such as allyl amine, to produce the isethionic acid allyl amine salt, which may then be esterified with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Scheme VI: Formation Of An Isethionic Acid Ethylenically Unsaturated Amine Salt

The prefened acids of the present invention are branched or linear alkylbenzene

sulfonic acids, alkyl sulfuric acid esters, alkoxylated alkyl sulfuric acid esters, α-sulfonated

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.

Other useful surfactants in accordance with the present invention include sulfonic acid salts of ethylenically unsaturated amines, derived from sultone precursors, such as cyclic alkyl sultones. Examples of these sultone-derived sulfonic acid salts (e.g., allyl amine salts) include 2-acetamidoalkyl-l -sulfonates and amino carboxy acid alkyl sulfonates, as shown in Scheme VII and Scheme VIII below.

Scheme VII: 2-Acetamidoalkyl-l -Sulfonic Acid Allyl Amine Salts

where R is C_4-24 alkyl. Scheme VIII: Amino Carboxy Acid Alkyl Sulfonic Acid Allyl Amine Salts

where R is C _-24 alkyl.

In general, 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

wherein R_\, R₂ 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.

Additionally, other examples of 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, Cι-C₂₄ alkyl allyl amine, Cι-C₂₄ alkyl ethoxylated and/or propoxylated allyl amine, Cι-C₂ dialkyl allyl amine, ethoxylated and/or propoxylated allyl amine diallyl amine, Cι-C₂₄ 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], 3-amino-2-butenethioamide, bis[4-(dimethylamino)- benzylidenejacetone, 1,4-butanediol bis(3-aminocrotonate), 3 -amino- 1-propanol vinyl ether, 2-(diethylamino)ethanol vinyl ether, 4-(diethylamino)cinnamaldehyde, 4-

(diethylamino)cinnamonitrile, 2-(diethylamino)ethyl methacrylate, diethyl (6-methyl-2- pyridylaminomethylene)maleate, 3-(dimethylamino)acrolein, 2-(dimethylamino)ethyl methacrylate, 4-dimethylaminocinnamaldehyde, 2-(dimethylamino)ethyl acrylate, 3- (dimethylamino)-2-methyl-2-propenal, 9-vinylcarbazole, N-vinylcaprolactam, 1- vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, allylcyclohexylamine, N- allylcyclopentylamine, allyl(diisopropylamino)dimethylsilane, 1-allylimidazole, l-vinyl-2- pynolidinone, N-[3-(dimethylamino)propyl]methacrylamide, 4-[4-

(dimethylamino)styryl]pyridine, 2-[4-(dimethylamino)styryl]pyridine, 2-[4-(l ,2-diphenyl-l- butenyl)phenoxy]-N,N-dimethylethylamine, 2-[4-dimethylamino)styryl]-benzothiozole, 5-[4- (dimethylamino)phenyl]-2,4-pentandienal, (dimethylamino-methylene)malononitrile, 4- dimethy laminocinnamonitrile, 4-(dimethy lamino)chalcone, [6-(3 ,3 -dimethylallylamino-purine riboside, 3,7-dimethyl-2,6-octadien-l-ylamine, 2-isopropenylaniline, isopropyl 3- aminocrotonate, S-{2-[3-(hexyloxy)benzoyl]-vinyl}glutathione, methyl 3-aminocrotonate, N- methylallylamine, N-methyl- l-(methylthio)-2-nitroetheneamine, oleylamine, tetrakis(dimethylamino)ethylene, 5-[(6,7,8-trimethoxy-4-quinazolinyl)amino]-l-pentanol nitrate ester, tris(2-methylallyl)amine, N,N,N',N'-tetramethyl-2-butene-l,4-diamine, S-{2-[3- (octyloxy)benzoyl] vinyl } -glutathione, 4,4 ' -vinylidene-(N,N-dimethylaniline), 2 ' ,5 ' - dimethoxy-4-stilbenamine, 3-(dimethylamino)propyl acrylate, 3-dimethylaminoacrylonitrile, 4-(dimethylamino)-cinnamic acid, 2-amino-l-propene-l,l,3-tricarbonitrile, 2-amino-4- pentenoic acid, N, N'-diethyl-2-butene-l,4-diamine, 10,l l-dihyro-N,N-dimethyl-5- methylene-5H-dibenzo[a,d]-cyclohepene-10-ethanamine maleate, 4-(dicyanomethylene)-2- methyl-6-(4-dimethyl-aminostyryl)-4H-pyran, N-ethyl-2-methylallylamine, ethyl 3-

aminocrotonate, ethyl-α-cyano-3-indoleacrylate, ethyl-3-amino-4,4-dicyano-3-butenoate, 1,3- divinyl-l,l,3,3-tetramethyldisilazane, N-(4,5-dihydro-5-oxo-l-phenyl-lH-pyrazol-3-yl)-9- octadecen-amide, and N-oleoyl-tryptophan ethyl ester, and mixtures thereof.

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. In the methods and compositions of the invention, amine salts are generally prefened over quaternary ammonium compounds.

Accordingly, the present invention utilizes surface active agents of the formula:

(R,)_n-Ar(SO₃-M⁺)_m wherein Ri is a saturated or unsaturated hydrocarbon group 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 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 (Rι)_n is at least 5. In a prefened embodiment 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. In another prefened embodiment, the surface active agent is of the formula:

wherein 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 (R₁)_n,-{Ar(SO₃-M⁺)_ml }-O-{Ar(SO₃-M⁺)_m2}-(R₂)_n2 wherein R] and R₂ 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. In a prefened embodiment, Ri is hydrogen and R 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, nl = 4, n2 = 1, and ml and m2 both equal one. In another prefened embodiment, 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. In another prefened embodiment, the surface active agent is of the formula:

wherein 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,-CH(SO₃ ^"M⁺)CO₂R₂ wherein Ri and R₂ are independently saturated or unsaturated hydrocarbon groups having from about 1- 24 carbon atoms; and wherein M⁺ is a conjugate acid of the nitrogenous base.

In a prefened embodiment, R_\ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms, R₂ is methyl, ethyl, or propyl, or a mixture thereof, and 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. In another prefened embodiment, the surface active agent is of the formula:

wherein n = 3-18.

The present invention further utilizes surface active agents of the formula:

R,-CH(SO₃ ^"M⁺)CO₂M⁺ wherein Ri is a saturated or unsaturated hydrocarbon group having from about 3-24 carbon atoms; and wherein M⁺ is a conjugate acid of the nitrogenous base. In a prefened embodiment, 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. In another prefened embodiment, the surface active agent is of the formula:

wherein n = 3-18.

The present invention further utilizes surface active agents of the formula: R,-CH(SO₃ ^"M⁺)C(O)O(CH₂CH(R')O)n R₂ wherein R_\ and R₂ 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. In a prefened embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 4-24 carbon atoms, R' is methyl or hydrogen, R₂ is methyl, ethyl, or propyl, and mixtures 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, and n = 1-100. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 2-18; and wherein n2 = 1 -20. The present invention further utilizes surface active agents of the formula:

R,-(SO₃ ^"M⁺) wherein R_\ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms and wherein M⁺ + is a conjugate acid of the nitrogenous base. In a prefened embodiment, R_\ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms, and 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. In another prefened embodiment, the surface active agent is of the formula:

wherein n = 5-17.

The present invention further utilizes surface active agents of the formula:

R, CO₂(CH₂)_nCH(SO₃ ^'M⁺)CO₂R₂ wherein Ri and R₂ 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. In a prefened embodiment, Ri and R₂ are independently saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms, n = 1-6, and 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. In another prefened embodiment, the surface active agent is of the formula:

wherein nl is zero or an integer of from 1- 17

The present invention further utilizes surface active agents of the formula:

R,CO₂(CH₂)_nSO₃ ^"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. In a prefened embodiment, R_\ is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms, n = 1-5, and M⁺ is a conjugate acid of the nitrogenous base, the nitrogenous base selected from the group consisting essentially of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, or a mixture thereof. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 2 -18.

The present invention further utilizes surface active agents of the formula: (R,)_n-Ar-O(CH₂CH(R^,)O)_rnSO₃ ^"M⁺ wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, and mixtures thereof; wherein R' is methyl or hydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base; wherein n = 1-5; wherein the total number of carbon atoms represented by (Rι)_n is at least 5; and wherein m is zero or an integer of from 1-100. In a prefened embodiment, R| 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 =

1, and m is zero or an integer of from 1-100. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 5 -18; and wherein n2 = 0-20.

The present invention further utilizes surface active agents of the formula:

R, O(CH₂CH(R' )O)_nSO₃-M⁺ wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R' is methyl or hydrogen; wherein n = 0-100; and wherein M⁺ is a conjugate acid of the nitrogenous base. In a prefened embodiment, R_\ is a saturated or unsaturated hydrocarbon group having from about 6- 24 carbon atoms, R' is methyl or hydrogen, n = 0- 100, and 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. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 5-18. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 5-18; and wherein n = 1-20. The present invention further utilizes surface active agents of the formula:

R,CO₂Tvl⁺ wherein R| is a saturated or unsaturated hydrocarbon group having from about 4-24 carbon atoms; and wherein M⁺ is a conjugate acid of the nitrogenous base. In a prefened embodiment, R] is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms, and 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. In another prefened embodiment, the surface active agent is of the formula:

CH₃(CH₂)_nC0₂ ^{" +}NH₃

wherein n = 5-18.

The present invention further utilizes surface active agents of the formula:

R, CON(R')(CH₂)„CO₂ ^"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. In a prefened embodiment, 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, R' is methyl, ethyl, propyl or hydrogen, and n = 2-5. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 2-18. The present invention further utilizes surface active agents of the formula:

R,CON(R')(CH₂)_nSO₃M⁺ 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. In a prefened embodiment, 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, R' is methyl, ethyl, propyl or hydrogen, and n = 2-5. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 2-18.

The present invention further utilizes surface active agents of the formula:

R, O(CH₂CH(R')O)_nCOCH₂SO₃ ^"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. In a prefened embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; R' is methyl or hydrogen, 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 = 0-100. In another prefened embodiment, the surface active agent is of the formula:

wherein nl = 5-17; and wherein n = 0-20.

The present invention further utilizes surface active agents of the formula:

R,O(PO₃)^x"M⁺ _y wherein R_\ is a saturated or unsaturated hydrocarbon group having from about 1- 24 carbon atoms, phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, an alkyl/alkoxylate substituted phenyl, an alkyl/alkoxylate substituted or poly-substituted polyphenyl, an alkyl/alkoxylate substituted or poly-substituted napthyl, an alkyl/alkoxylate substituted or poly-substituted polynapthyl, an alkyl/alkoxylate substituted or poly-substituted styryl, or an alkyl/alkoxylate substituted or poly-substituted polystyryl group, and mixtures thereof; wherein M⁺ is a conjugate acid of the nitrogenous base; wherein x = 1 or 2; and wherein y = 1 or 2.

The present invention further utilizes surface active agents of the formula:

[R, O(CH₂CH(R')O)_m]_nP(O)_p ^χ-M⁺ _y wherein R_\ is a saturated or unsaturated hydrocarbon group having from about 1- 24 carbon atoms; 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-(dimethylamino)ethyl acrylate, and mixtures thereof; m = 0 -100; wherein n = 1 or 2; wherein p = 2 or 3; wherein x = 1 or 2; and wherein y = 1 or 2.

The present invention further utilizes surface active agents of the formula:

[(R,)_nArO(CH₂CH(R')O)_m]_qP(O)_p ^χ-M⁺ _y wherein 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-

(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n = 1-4; wherein m = 0 -100; wherein q = 1 or 2; wherein p = 2 or 3; wherein x = 1 or 2; and wherein y = 1 or 2.

Although less prefened, the present invention may utilizes polymerizable surface active agents which are quaternary ammonium salts of the general formula:

wherein R|, R₂, R₃, and R₄ 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 R₁-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. Additionally, 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, R₂, 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 Rι-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. Additionally, 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.

Scheme IX: Amine Oxide-Derived Polymerizable Surface Active Agents

The present invention further encompasses quaternary halide-derived polymerizable surface active agents, formed as shown in Scheme X, wherein R_\, R₂, R₃ 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 Rι-R₃ 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. Additionally, 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.

"Reverse" Polymerizable Surface Active Agents Although somewhat less prefened, the 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 Cι-C₂₄ alkyl group. By substantially saturated nitrogenous base, it is meant that the nitrogenous base contains less than about 5% unsaturation in the alkyl group(s). In general, the ethylenically unsaturated acids of the present invention are any sulfonic acids, carboxylic acids, or phosphoric acids which contain at least one unsaturated moiety. More specifically, 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 acid sulfonates, unsaturated alkoxylated carboxylic acid sulfonic acids, unsaturated polycarboxylic acids, unsaturated polycarboxylic acid polysulfonic acids, unsaturated alkoxylated polycarboxylic acid polysulfonic acids, unsaturated phosphoric acids, unsaturated alkoxylated phosphoric acids, unsaturated polyphosphoric acids, and unsaturated alkoxylated polyphosphoric acids, unsaturated fluorinated phosphoric acids, unsaturated phosphoric acid esters of oils, unsaturated phosphinic acids, unsaturated alkylphosphinic acids, unsaturated aminophosphinic acids, unsaturated polyphosphinic acids, unsaturated vinyl phosphinic acids, unsaturated phosphonic acids, unsaturated polyphosphonic acids, unsaturated phosphonic acid

alkyl esters, unsaturated α-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.

Other 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,

unsaturated α-sulfonated alkyl ester acids, unsaturated α-sulfonated ester diacids, unsaturated

alkoxylated α-sulfonated alkyl ester acids, unsaturated α-sulfonated dialkyl diester acids,

unsaturated di-α-sulfonated dialkyl diester acids, unsaturated α-sulfonated alkyl acetate 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 diamides, unsaturated alkyl phenol sulfuric acid esters, unsaturated alkoxylated alkyl phenol sulfuric acid esters, unsaturated alkylated cycloalkyl sulfuric acid esters, unsaturated alkoxylated alkylated cycloalkyl sulfuric acid esters, unsaturated dendritic polysulfonic acids, unsaturated dendritic polycarboxylic acids, unsaturated dendritic polyphosphoric acids, unsaturated sarcosinic acids, unsaturated isethionic acids, and unsaturated tauric acids, and mixtures thereof.

Additionally in accordance with the present invention, 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.

In general, 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 Cι-C₂ alkyl group. Preferably, 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 The present invention encompasses the use of 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.

Additional auxiliary polymerizable surfactants useful herein, for example, 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 incoφorated herein in their entirety).

Supplemental Surface Active Agents Generally, optional non-polymerizable surface active agents may be utilized in the present invention. These 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, incoφorated herein by reference. Generally, 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 block polymers, polyhydroxy fatty acid amides, amine oxides and mixtures thereof. Further, exemplary, non-limiting classes of useful supplemental nonionic surface active agents are listed below:

1. The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates 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. In a prefened embodiment, 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. Commercially available nonionic surfactants of this type

include Igepal® CO-630, marketed by Stepan Company, Canada; and Triton® X-45,

X-l 14, X-100 and X-102, all marketed by the Union Carbide Company.

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol 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

available nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation

products of C_{1 1}-C₁₅ linear alcohol with 9 moles of ethylene oxide), Tergitol® 24-L-6

NMW (the condensation products of Cι₂-Cι₄ primary alcohol with 6 moles of ethylene oxide with a nanow molecular weight distribution), both marketed by Union Carbide

Coφoration; Neodol® 91-8 (the condensation product of C₉-Cn linear alcohol with 8

moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of Cj₂-C₁₃ linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of

Cι₄-Ci₅ linear alcohol with 7 moles of ethylene oxide), Neodol® 91-6 (the condensation product of C₉-Cn linear alcohol with 6 moles of ethylene oxide),

marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of Ci -Ci₅ linear alcohol with 9 moles of ethylene oxide), marketed by the Procter and

Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. 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

commercially available Pluronic® surfactants, marketed by BASF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists 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.

5. 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. 6. Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Lenado, issued Jan. 21,

1986, incoφorated herein by reference, having a 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. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) 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.

7. An ethyl ester ethoxylate and/or alkoxylate such as those described in U.S. Pat. No. 5,220,046, incoφorated 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

Af ³, Ga⁺³, In⁺³, Sc⁺³, La⁺³ and Mn⁺³. Optionally, and less desirably, there can be a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The prefened alkyleneoxide is ethylene oxide. 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

1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, 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.

Examples of suitable supplemental amphoteric surface active agents are selected from the group comprising alkyl glycinates, propionates, imidazolines, amphoalkylsulfonates sold

as "Miranol"® by Rhone Poulenc, N-alkylaminopropionic acids, N-alkyliminodipropionic

acids, imidazoline carboxylates, N-alkylbetaines, amido propyl betaines, sarcosinates, cocoamphocarboxyglycinates, amine oxides, sulfobetaines, sultaines and mixtures thereof. Additional suitable 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.

Examples of supplemental amine oxide surface active agents which are generally suitable for use in the present invention are alkylamine and amidoamine oxides. Examples of supplemental betaine and sultaine surface active agents which are suitable for use in the

present invention are alkyl betaines and sultaines sold as "Mirataine"® by Rhone Poulenc ,

"Lonzaine"® by Lonza, Inc., Fairlawn, NJ. Examples of 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.

Examples of 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.

Examples of suitable supplemental cationic surface active agents are disclosed in the following documents, all incoφorated 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, Hilfer, 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. 4,387,090, Bolich, Jr., issued June 7, 1983. Examples of 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 R₂ have predominately from about 16 to about 18 carbon atoms). Examples of 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, incoφorated 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. Additionally, carbon atoms that are part of a hydrophilic moiety, e.g., carbon atoms in a hydrophilic polyoxyalkylene (e.g.,-CH₂-CH₂-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. In general, the alkyl portion of any hydrophilic moiety is preferably a C|-C alkyl. 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.

Among the supplemental cationic surface active agents useful herein are those of the general formula:

wherein Ri, R₂, R , and R₄ 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 Rι-R groups contains one or more hydrophilic moieties selected from the group comprising alkoxy (preferably Cι-C₃ alkoxy), polyoxyalkylene (preferably Ci- C polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester and combination thereof. Preferably, the cationic conditioning surfactant contains from about 2 to about 10 nonionic hydrophile moieties located within the about stated ranges. For puφoses herein, 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.

Other 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. Specific examples include 2-heptadecyl-4,5-dihydro-lH-imidazol-l-ethanol, 4,5- dihydro-l-(2-hydroxyethyl)-2-isoheptadecyl-l-phenylmethylimidazolium chloride, and l-[2- oxo-2-[[2-[(l-oxoctadecyl)oxy]ethyl]amino]ethyl] pyridinium chloride. Salts of primary, secondary and tertiary fatty amines are also prefened supplemental cationic surfactant materials. 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.

The 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, 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, alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids, vinyl phosphinic

acids, phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters, α-phosphono

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.

Other 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

sulfuric acid esters, α-sulfonated alkyl ester acids, α-sulfonated ester diacids, alkoxylated

α-sulfonated alkyl ester acids, α-sulfonated dialkyl diester acids, di-α-sulfonated dialkyl

diester acids, α-sulfonated alkyl acetate acids, primary and secondary 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 alkylated cycloalkyl sulfuric acid esters, dendritic polysulfonic acids, dendritic polycarboxylic acids, dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, and tauric acids, and mixtures thereof.

Additionally in accordance with the present invention, 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.

In a prefened embodiment of the present invention, 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.

In another embodiment of the present invention, 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. In this embodiment, 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. Although somewhat less prefened, in a further embodiment of the present invention, 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.

Initiators and Additives

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.

A further additive which may be added to the mixture contents is a conventional chain transfer agent, such as an alkyl polyhalide or mercaptan. Examples of suitable chain transfer agents include bromoform, carbon tetrachloride, carbontetrabromide, bromoethane, Cι-C| alkyl mercaptans, e.g., dodecylmercaptan, thiophenol, and hydroxyalkyl mercaptans, e.g., mercaptoethanol.

Optional Water Immicsible Solvents Although less preferable, small amounts of water-immiscible solvents may be used in the agricultural formulations of the present invention. Specific examples of 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 of the methyl ether of dipropylene glycol, ketones such as isophorone and trimethyl cyclohexanone (dihydroisophorone) and the acetate products such as hexyl, or heptyl acetate. The prefened organic liquids are xylene, propyl benzene fractions, dihydroisophorone, and alkyl acetates.

Agricultural Technicals Agriculatural technicals useful in the present invention include pesticides, herbicides and fungicides. 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, chloφyrifos, chloφhoxim, chloφyrifos-methyl, fenamiphos, cyanophos, fenobucarb, *cyfluthrin, gamma-HCH,

*cypermethrin, methidathion, *deltamethrin, parathion methyl, *dicofol, phosalone, dioxabenzafos, phosfolan, dioxacarb, phosmet, *endosulfan, promecarb, EPN, quinalphos,

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. Other 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. 30,563, which are incoφorated herein by reference, and l-[3,5-dichloro-4-((5-trifluoromethyl)-3-chloro-2- pyridyloxy)phenyl]-3-(2,6-difluorobenzoyl) urea (common name Chlorfluazuron): the organophosphorous insecticides described in U.S. Pat. Nos. 3,244,586; 4,429,125; 4,654,329 and 4,729,987 which are incoφorated herein by reference, chloφyrifos and chloφyrifos methyl: the pyrethroid insecticides such as cypermethrin, permethrm and fenvalerate:the aryloxyaryl herbicides described in U.S. Pat. Nos. 4,550,192: 4,551,170 and 4,750,931 which are incoφorated herein by reference, 2-(4-((5-trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propanoic acid; 2-(4-((3-chloro-5-trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propanoic acid, methyl ester: 2-(4-((3-chloro-5-trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propanoic acid, ethyl ester: and 2-(4-((3-fluoro-5-trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propanoic acid, methyl ester: and the sulfonamide herbicides described in U.S. Pat. Nos. 4,731,446: 4,740,233: 4,741,764 and 4,755,212 which are incoφorated herein by reference, especially N-(2,6-dichlorophenyl)-5,7-dimethoxy- 1,2,4- triazolo (l,5a)pyrimidine-2-sulfonamide: N-(2,6-dichloro-3-methylphenyl)-5,7-dimethoxy- 1,2,4-triazolo (l,5a)-pyrimidine-2-sulfonamide; N-(2,6-dichloro-phenyl)-5-methyl-7- methylthio-l,2,4-triazolo (l,5a)pyrimidine-2-sulfonamide; N-(2-trifluoromethylphenyl)-5- methyl-7-methylthio-l,2,4-triazolo-(l, 5a) pyrimidine-2-sulfonamide: N-(2,6-dichloro-3- methylphenyl)-7-methoxy-5-methyl-l,2,4-triazolo (l,5a)-pyrimidine-2-sulfonamide: and N- (2,6-dichloro-3-methylphenyl)-7-ethoxy-5-methyl-l,2,4-triazolo (l,5a)pyrimidine-2- sulfonamide.

Fungicidal substances suitable for use in the composition in accordance with the invention include, for example benalaxyl myclobutanil

bupirimate nuarimol

carboxin oxycarboxin

dodemoφh ergosterol

dodine fenarimol ditalimfos penconazole prochloraz tolclofos-methyl

triadimefon triadimenol and mixtures thereof.

Herbicidal substances suitable for use in the composition in accordance with the invention include, for example aclonifen chloφropham 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 oxadiazon

*oxyfluorfen

*pendimethalin. and mixtures thereof. Of the above active materials, those indicated * have a water solubility of less than

500 ppb, and thus are of direct relevance only to those aspects of the invention concerned with the nature of the polymeric latex.

Other 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.

The 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.

Similarly conventional pesticide additives such as adjuvant solvents, surfactants for increasing penetration of the active substances or salts may be incoφorated into the compositions to maintain or improve biological efficacy of the composition. These may be incoφorated into the oil phase or aqueous phase as appropriate. All documents, e.g., patents and journal articles, cited above or below are hereby incoφorated by reference in their entirety.

In the following examples, all amounts are stated in percent by weight unless indicated otherwise. One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein. All documents, e.g., patents and journal articles, cited above or below are hereby incoφorated by reference in their entirety.

As used in the Examples appearing below, the following designations, symbols, terms and abbreviations have the indicated meanings:

Material Definition

Polystep® A- 13 Linear dodecylbenzene sulfonic acid (commercially available from

Stepan Company, Northfield Illinois)

Polystep® A- 16 Branched dodecylbenzene sulfonic acid, sodium salt (commercially

available from Stepan Company, Northfield Illinois)

Polystep® A-l 7 Branched dodecylbenzene sulfonic acid (commercially available from

Stepan Company, Northfield Illinois)

Cedephos CP-610 Nonyl Phenol 9-EO Phosphoric Acid Ester (commercially available from Stepan Company, Northfield Illinois) 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

operated at 25 °C and 60 φm.

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

remove all volitiles, and subsequently weighing the residue. The pH of each solution was measured using an Orion 210 pH meter. Particle size was measured using a Nicomp 370,

[submicron analyzer , (up to 2 microns)]. 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).

In the following examples, all amounts are stated in percent by weight of active material unless indicated otherwise. One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein.

Latex Examples

Example 1 :

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 dodecylbenzenesulfonic acid (ADDBS), is prepared as follows. About 254 g of deionized water and about 10.6 g of ADDBS (as a 22% 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

about 80-82°C. 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

continued agitation, during which time there is an exotherm of about 7-10°C. After the exotherm is complete, about 299 g of the monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture), 64.5 g of the ammonium persulfate solution (the remaining 80 %) , and 15.55g of ADDBS (as the 22% active aqueous solution) are simultaneously charged to the reactor over a period of 2 hours with continued agitation, while

keeping the reactor contents at a 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 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

II.

Example 2 (^"Comparative Example):

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

about 80-82°C. 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, 15.5 g of a solution of ammonium persulfate (20 % of the total solution of 1.9 g of ammonium persulfate dissolved in 75.6 g of water), is added to the reactor over a period of about 5 minutes with

continued agitation, during which time there is an exotherm of about 3-5°C. After the

exotherm is complete, about 299 g of the monomer mixture (the remaining 80%) and 62 g of the ammonium persulfate solution (the remaining 80%) are simultaneously charged tot he reactor over a period of 2 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

with continued agitation, for about 15 minutes. After this 15 minute period, 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 II.

Example 3:

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

is purged with nitrogen (99% pure), and heated to about 75 77°C. The temperature of the

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. After 10 minutes, 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

exotherm of about 5-8°C. After the exotherm is complete, about 299 g of the monomer

mixture (the remaining 80% MMA/BA MMA monomer mixture), 60.7 g of the ammonium persulfate solution (the remaining 80 %), and 15.3 g of the allyl amine salt of Cedephos CP- 610 (as a 20% active aqueous solution) are simultaneously charged to the reactor over a period of 2 hours with continued agitation, while keeping the reactor contents at a

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

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 II. 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

nitrogen (99% pure), and heated to about 75 77°C. The temperature of the reactor contents is

adjusted to about 71-74°C, and about 75 g of the monomer mixture (20% of a total of 375 g of

the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 15 g of a solution of ammonium persulfate (20% of the total solution of 1.9 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 exotherm of about 8-

10°C. After the exotherm is complete, about 300 g of the monomer mixture (the remaining

80%) MMA/BA/MMA monomer mixture), 61.5 g of the ammonium persulfate solution (the remaining 80%o), and 15.3 g of the propylamine salt of Cedephos CP-610 (as a 20% active aqueous solution) are simultaneously charged to the reactor over a period of 2 hours with

continued agitation, while keeping the reactor contents at a temperature of about 78-80°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 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 II. Example 5

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

is purged with nitrogen (99% pure), and heated to about 70-73°C. The temperature of the

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. After 10 minutes, 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

exotherm of about 2-3°C. After the exotherm is complete, about 299 g of the monomer

mixture (the remaining 80% MMA BA/MMA monomer mixture), 61.5 g of the ammonium persulfate solution (the remaining 80%), and 29.2 g of the ALA (as a 20% active aqueous solution) are simultaneously charged to the reactor over a period of 2 hours with continued

agitation, while keeping the reactor contents at a temperature of about 78-81°C. The reactor

temperature is then elevated to about 83-85°C with continued agitation, for about 15 minutes.

After this 15 minute period, 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 II.

Example 6 (Comparative Example :

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

is purged with nitrogen (99% pure), and heated to about 75-77°C. The temperature of the

reactor contents is adjusted to about 71-73°C, and about 7 g of the monomer mixture (2%> of a

total of 373 g of the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 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

exotherm of about 2-3°C. After the exotherm is complete, about 366 g of the monomer mixture (the remaining 98% MMA BA/MMA monomer mixture), 61.5 g of the ammonium persulfate solution (the remaining 80%), and 28.4 g of the PLA (as a 20% active aqueous solution) are simultaneously charged to the reactor over a period of 2 hours with continued

agitation, while keeping the reactor contents at a temperature of about 79-82°C. The reactor

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

to about 65-68°C. The temperature of the reactor contents is adjusted to about 63-65°C, and

about 73.7 g of the monomer mixture (20%> of a total of 369 g of the VA/BA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 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 5 minutes with continued

agitation. The temperature of the reactor is increased to about 82-84°C. Evidence of

polymerization is observed by the appearance of blue tint in the reaction contents and a slight

exotherm of 1 -2°C. 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

keeping the reactor contents at a temperature of about 78-82°C. The reactor temperature is

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.

Example 8 (Comparative Example): A vinylacetate/butyl acrylate (VA BA) co-polymer (in a weight ratio of about

79.1:20.9), in combination with the propyl amine salt of dodecylbenzenesulfonic acid (PDDBS) is prepared as follows. About 162 g of deionized water and about 5.4 g of PDDBS (as a 23% 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 about 65-68°C. The

temperature of the reactor contents is adjusted to about 62°C, and about 5.0 g of the monomer

mixture (2% of a total of 245 g of the VA BA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 10.1 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 15 minutes with continued agitation. The temperature of the

reactor is increased to about 82-84°C. Evidence of polymerization is observed by the

appearance of blue tint in the reaction contents and a slight exotherm of 2-4°C. The

temperature of the 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

to about 82-84°C with continued agitation, for about 15 minutes. After this 15 minute period,

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.

Example 9:

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. With

temperature of the reactor contents is adjusted to about 60-63°C, and about 73.7 g of the monomer mixture (20% of a total of 369 g of the VA/BA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 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 5 minutes with continued agitation. The

temperature of the reactor is increased to about 82-84°C. Evidence of polymerization is

observed by the appearance of blue tint in the reaction contents and a slight exotherm of 1 -

2°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

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.

Example 10

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. About 251 g of deionized water and about 1.5 g of ADDBS (as a 19% active aqueous solution), 0.9 g of PDDBS (as a 23 % active aqueous solution), and 0.3 g of sodium hydrogen carbonate 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 about 65-68°C. The temperature of the

reactor contents is adjusted to about 63-65°C, and about 10.3 g of the monomer mixture (2%

of a total of 513 g of the VA/BA monomer mixture in the ratio above) is added to the reactor. After 15 minutes, 13.7 g of a solution of ammonium persulfate (20% of the total solution of 2.0 g of ammonium persulfate dissolved in 66.5 g of water) and 13.7 g of a solution of sodium metabisulfite (20% of the total solution of 0.83 g of sodium metabisulfite dissolved in 67.8 g of water) is added to the reactor over a period of about 5 minutes with continued agitation. Evidence of polymerization is observed by the appearance of blue tint in the reaction contents

and a slight exotherm of 1 -2°C. 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

68 - 72°C. 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

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.

Example 11

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. With

agitation, the reactor is purged with nitrogen (99% pure), and heated to about 77 - 79°C.

Next, about 75 g of the monomer mixture (20% of a total of 376 g of the MMA BA/MMA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 15.0 g of a solution of ammonium persulfate (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 72.9 g of water) is added to the reactor over a period of about 4 minutes with

continued agitation, during which time there is an exotherm of about 12-14°C. After the

exotherm is complete, about 301 g of the monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture), 59.8 g of the ammonium persulfate solution (the remaining 80 %) , and 22.0 g of AAES-3 (as the 22% active aqueous solution) are charged to the reactor over a period of 2 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 with continued agitation, for about 15 minutes. After this 15 minute period,

the reactor is cooled to about 30°C. 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: Solids 48.41%

Particle size (nm) Vol (50%) 95nm. pH 2.43

Visc.(3/60) 140.00 (centipoise)

Coagulum 0.36g (<0.05% on total batch weight).

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

is purged with nitrogen (99% pure), and heated to about 77 - 79°C. Next, about 77 g of the

monomer mixture (20% of a total of 378 g of the MMA/BA/MMA monomer mixture in the ratio above) is added to the reactor. After 10 minutes, 15.4 g of a solution of ammonium persulfate (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 75.0 g of water) is added to the reactor over a period of about 4 minutes with continued agitation,

during which time there is an exotherm of about 7-8°C. After the exotherm is complete, about 301 g of the monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture), 61.6 g of the ammonium persulfate solution (the remaining 80 %>) , and 33.7 g of AS (as the 17.2% active aqueous solution) are charged to the reactor over a period of 2 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 with continued agitation,

for about 15 minutes. After this 15 minute period, the reactor is cooled to about 30°C. 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:

Solids 48.41%

Particle size (run) Vol (50%) 95nm. pH 2.43 Visc.(3/60) 140.00 (centipoise)

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.

Time (Seconds)

Latex Surfactant 5 20 40 60

AmDDBS (non-polymerizable) (Contact Angle) 98° 74° 51° 27°

ADDBS (polymerizable) (Contact Angle) 125° 125° 125° 125°

Without being bound by any particular theory, 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, as in the case of the ADDBS derived latex, indicates the desirable result whereby water is unable to penetrate the hydrophobic film.

In a test similar to the contact angle measurements, 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. As observed in the results shown below, water undesirably, readily penetrated through the film and absorbed into the paper in a few seconds for the latex derived from the AmDDBS surfactant. However, 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).

Time (Seconds) Latex Surfactant 5 20 40 60

AmDDBS (non-polymerizable) (penetration absorption) slight total total total

ADDBS (polymerizable) (penetration/absorption) none none none none

The 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. obtained, the better the adhesion properties of the latex. 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

temperature (i.e. 25°C) for three days under 0.25 p.s.i. external pressure. Aluminum and steel blocks were prepared by sanding with extra fine 220 grit paper until smooth to the touch. A weighed amount of each latex (0.5 g) was placed on one surface of one block and another block place on top for three days. Failure was determined by visual inspection, with the results indicated below.

Latex Surfactant Adhesive Failure (p.s.i AmDDBS (non-polymerizable) 65

ADDBS (polymerizable) 170

The 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. After a period of 6 months, 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.

Latex Absorbance

Latex Surfactant 350 nm 420 ran

AmDDBS (non-polymerizable) 16.9 5.3

ADDBS (polymerizable) 10.0 2.5 The scrubability 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 improved scrubability characteristics, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid,

AmDDBS). Scrubability of the latexes was evaluated using ASTM scrub test D2486. Seven

Star Acrylic Flat House Paint, 103A100 White, from Ace Hardware was utilized in the testing. The ADBBS- and AmDDBS-derived latexes were individually added to the paint in a ratio of 2:1 (latex:paint). FTIR comparisons were conducting by casting latex films on glass, derived from both

ADDBS and AmDDBS. The films were dried at room temperature for several days, removed from the glass and aged at room temperature, at approximately standard atmospheric conditions, for six months. The films were individually placed on a ZnSe plates and the FTIR spectra recorded. Peak heights were measured on the absorbance peak located at 1035 cm^"1 (i.e. the S=O stretch peak) for each film. It has been discovered that the latex prepared in Example 1 (using ADDBS) possess a much lower peak height absorbance in the FTIR spectrum, as compared to the latex prepared according to Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS). Without being bound by any particular theory, a lower the peak height absorbance indicates a desirable characteristic of the latex, whereby the individual surfactant molecules are not present at the surface of the latex film, i.e. they have not migrated to the surface of the film.

Latex Surfactant Latex FTIR Absorbance (x 10^"4)

AmDDBS (non-polymerizable) 73 ADDBS (polymerizable) 29 Agricultural Formulations

The oil phase (i.e. agricultural technical + optional supplemental surface active agent; i.e. co-surfactant, and optional water immissible solvent) 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. They also have the ability in many cases, since they contain film-forming latexes, to be utilized in those areas where film forming is a desirable effect, such as in seed treatments and pest control in dwelling places. They are however particularly suitable for an intended for use on growing crops, and to locations in which agricultural crops are to be grown, particulary cereals and the like. Agricultural compositions of the invention show improved long term stability, as compared with the compositions of EP 0080516. Example 1

Formulations of NMS (non-migrating surfactnat: polymerizable surface active agent- derived) latex 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). 15 g of DI water was blended into each latex prior to addition of the pesticide + co- surfactant. The oil phase was added slowly to the latex and water solution while the latex was being stined using a magnetic stir bar and stir plate. After oil phase addition was complete, each mixture was stined for 5 minutes, and then transfened to 100 mL conical centrifuge tubes. After 24 hours, the separation was measured. The results are in the following table:

Traditional Latex NMS Latex mL of separation @ 24 hrs. 0.25 0.01 Description of separation: Oil creamy

The samples were monitored for another 13 days, at which time the traditional latex formulation had formed 0.7 mL of oily separation, but the NMS latex had not formed any oily separation. The NMS latex had formed some layers of creamy stratification but when the tube was inverted through 10 inversions the mixture was uniform. The 0.7 mL of oily separation in the traditional surfactant latex did not go into solution even after more than 20 inversions of the tube. Formulations of NMS latex show superior physical stability compared to migrating latexes.

Example 2

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, and Latex Example #3, also called AU-9 latex) containing chloφyrifos 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 chloφyrifos in the solvent plus co-surfactant solution was 65% w/w. Each formulaton contained 25 g of the latex, 15 g. of chloφyrifos 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. After 60 days of storage, there were noticeable changes in the migrating surfactant containing latexes. Both samples developed a thick layer of yellow colored coagulum on the bottom of the bottles. The coagulum was removed, drained and weighed. The results are in the following table. Formulation / surfactant Residue wt. (g) Particle Size of latex Latex Example #1 -Derived 0 98 ran

Traditional Surfactant 2.23 157 ran

Latex Example #3-Derived 0 95 ran

Traditonal Surfactant 6.21 91 run Both of the NMS latex samples remained uniform, and had excellent dispersion properties after the 60 day storage time. Example 3

It is possible to achieve a higher active ingredient content product using non-migrating latexes in pesticide formulations instead of traditional type latexes. The higher concentration products also suφrisingly 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.

The amount of acetochlor that was added, and the number of inversions required to disperse 1 g. of product in 99 mL of 1000 ppm (as CaCO3) test water is in the table that follows.

Traditional Surfactant Latex Latex Example #3 Latex

Weight of Latex: 12.5 g 12.5 g

Oil phase weight added: 21.35 g 26.95 g

Ratio of oil phase to polymer solids: 3.7:1 4.7:1

# inversions needed to disperse 1 g. in 99 mL of test water: 45 12

The dispersions show only a trace of creamy separation after 1 hour at room

temperature. Example 4

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.

Example 5

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.

The formulation compositions are below:

Ingredient Formulation Formulation

Latex 25 g 25 g

DI water 15 g 15 g Metolachlor TG 12.5 g

Trifluralin Stock Solution 12.5 g

Makon 10 1.39 g 1.39 g

These formulations remained stable, showing no separation for 4 months at room temperature.

Example 7

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:

Active Ingredient 14 day separation Latex acetochlor trace AU-7 chloφyrifos slight trace AU-7 trifluralin trace AU-7 metolachlor slight trace AU-7

The separation rates shown above are what typically would show up after 24 hours for an emulsifiable concentrate type formulation. Example 8

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.

Basic formulation: 50% Latex (AU-1 or AU9); 30% Oil phase (stock solution containing

10% Makon 10); and 20% DI water.

Chloφyrifos 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:

Active Ingredient Latex Separation

Metolachlor AU-1 None Metolachlor AU-9 Slight trace

Acetochlor AU-1 Slight trace

Acetochlor AU-9 Slight trace

Chloφyrifos AU-1 Slight trace

Chloφyrifos AU-9 None Example 9

NMS latexes show excellent stability at dilutions below 1 :200. Chloφyrifos formulations were prepared by blending a chloφyrifos 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

1% 0 0

0.1% 0 0

0.01% 0 0

0.001% 0 0

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.

Pressure and separation readings for the Metolachlor EC Time (Min.) Pressure (PSI) Separation @ 30 minutes 0 20 Sl. Trace

10 20 SI. Trace

20 19 SI. Trace

30 18.5 SI. Trace

40 18 SI. Trace

50 18 SI. Trace

60 18 SI. Trace

Separation and pressure readings for Metolachlor latex formulation NMS-based Time (Min.) Pressure (PSI) Separation @ 30 minutes

0 20 0

10 20 0

20 20 0

30 20 0 40 19.5 0

50 19 0

60 19 0

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. At that time, the product was observed for any changes in appearance and the dispersion check was once again performed. At no time during the study were any physical changes detected. The dispersion stability was also very good, showing no more than a trace of separation after 3 hours. When the cylinder was re-inverted after the separation reading, the residue was easily re-dispersible.

From the foregoing, it will be appreciated that although specific embodiments of the invention have been described herein for puφoses of illustration, various modifications may be made without deviating from the spirit or scope of the invention.

Claims

What is claimed is:

1. An agricultural formulation comprising a) a polymer latex comprising: i) at least one monomer unit; and ii) 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 in the form of an amine salt comprising: i) at least one acid, wherein the acid is a sulfonic acid, a sulfuric acid ester, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and ii) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety; and wherein the ethylenically unsaturated monomer and the polymerizable surface active agent have polymerized to form the polymer latex; and b) an agricultural technical.

2. A agricultural formulation according to claim 1, additionally comprising a water immisible solvent, or a secondary surface active agent, or a mixture thereof.