WO1999018786A1 - Method and composition for dispersing an insoluble material in aqueous solution - Google Patents

Method and composition for dispersing an insoluble material in aqueous solution Download PDF

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Publication number
WO1999018786A1
WO1999018786A1 PCT/AU1998/000853 AU9800853W WO9918786A1 WO 1999018786 A1 WO1999018786 A1 WO 1999018786A1 AU 9800853 W AU9800853 W AU 9800853W WO 9918786 A1 WO9918786 A1 WO 9918786A1
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WIPO (PCT)
Prior art keywords
comonomer
copolymer
vinyl
group
cyclic
Prior art date
Application number
PCT/AU1998/000853
Other languages
French (fr)
Inventor
Andrew Francis Kirby
Rodney Walter Parr
Phillip Robert Tudor
David Hayshiv Parris
Original Assignee
Huntsman Surfactants Technology Corporation
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Publication date
Application filed by Huntsman Surfactants Technology Corporation filed Critical Huntsman Surfactants Technology Corporation
Priority to AU95242/98A priority Critical patent/AU9524298A/en
Publication of WO1999018786A1 publication Critical patent/WO1999018786A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

  • the present invention relates generally to dispersants, for use in agricultural applications, in particular the present invention relates to methods for the dispersion of insoluble material with
  • copolymeric dispersants which dispersions are formed with improved dispersibility and show
  • the present invention also relates to methods of producing
  • dispersible formulations the formulations per se and methods of treating substrates with
  • the active principle is typically
  • SC suspension concentrate
  • WP wettable powder
  • Pesticides Analytical Council (CIPAC Handbook Volume 1) defines methods that can be used
  • MT 15.1 acceptable suspensibility
  • MT 59.3 degree of agglomeration
  • dispersible granule (WG) formulations generally require the addition of standard dispersant
  • copolymer surfactants based on an hydrophobic moiety plus ethyleneoxide. Also used are
  • anionic surfactants used include sulphonated derivatives of arylformaldehyde
  • Dispersants for WP and WG formulations are usually limited by the requirement that the
  • dispersant be solid at ambient temperatures, be non-gelling and not dissolve the active
  • anionic dispersants are preferred.
  • Known effective dispersants for WP and WG formulations include sulphonated alkylnaphthalene/formaldehyde condensate salts and lignosulfonate salts.
  • ⁇ -Olefin-polycarboxylate copolymers are well known as dispersants in a wide range of
  • EP 201417 describes the use of
  • JP 62036302 describes
  • copolymers having a molecular weight range of from 5000-20000 for use with granular
  • dispersant comprising a water soluble agriculturally acceptable derivative of a
  • copolymer or an agriculturally acceptable salt thereof wherein said copolymer
  • said first comonomer is selected from the group consisting of alicyclic
  • dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer
  • said first comonomer is selected from the group consisting of alicyclic
  • an agrochemical formulation comprising the steps of: (i) combining at least one insoluble material, with at least one dispersant comprising
  • dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer
  • dispersant comprising providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally
  • agrochemical formulation comprising the steps of:
  • copolymer comprises residues of at least one first comonomer and at
  • At least one second comonomer wherein said first comonomer is selected from the group
  • formulation comprising at least one insoluble material and at least one dispersant comprising
  • first comonomer one first comonomer and at least one second comonomer wherein said first comonomer is
  • olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not
  • treatment of a substrate with an insoluble material comprising the following steps: (i) preparing a formulation comprising providing a formulation comprising at least one
  • insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof
  • copolymer comprises residues of at least one first comonomer and at
  • At least one second comonomer wherein said first comonomer is selected from the group
  • the first comonomer for use in the present invention may be an alicyclic monomer having
  • alicyclic monomer an aliphatic cyclic monomer containing moieties such as a cyclic alkyl, cyclic alkenyl
  • exo-cyclic is meant an alkylidene substituted cyclic structure.
  • Alicyclic monomers having a polymerizable exo-cyclic double bond may optionally
  • present invention may include, for example, ⁇ -pinene, 5-ethylidene-2-norbonene. methylene cyclohexane and methylene cyclopentane.
  • the first comonomer for use in the present invention may be an alicyclic monomer having
  • alicyclic monomer is as hereinabove
  • endo-cyclic is meant the polymerizable double bond has both ends (or termini) forming part of the cyclic structure of the alicyclic monomer.
  • Alicyclic monomers having a polymerizable endo-cyclic double bond may optionally be
  • Alicyclic monomers having a polymerizable endocyclic double bond may
  • cyclopentadienes substituted and unsubstituted dicyclopentadienes , cyclohexenes, furans and
  • dicyclopentadiene and dimethyldicyclopentadiene dicyclopentadiene and dimethyldicyclopentadiene.
  • the first comonomer for use in the present invention may be an ⁇ -olefin having at least one
  • cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene.
  • ⁇ -olefin is meant an olefinic compound having a terminal double bond.
  • Suitable cyclic substituents include cyclopentane, cyclohexane, and other cylcoaliphatics, heterocyclics, hetro aromatic s and polyaromatics.
  • suitable ⁇ -olefinic compounds include limonene and similar te ⁇ enes, vinyl cyclohexanes, vinyl
  • ⁇ -olefin monomers include d-limonene, vinyl
  • the second monomer for use in the present invention comprises an ⁇ , ⁇ -unsaturated oxyacid
  • ⁇ , ⁇ - oxyacids comprise a polymerizable double bond adjacent to one or more
  • second comonomers for use in the present invention include fumaric acid, maleic acid and
  • second type is maleic anhydride.
  • the dispersants are agriculturally acceptable salts or water-soluble agriculturally acceptable
  • alkali metal salts such as the sodium or potassium salt of the copolymer.
  • Ammonium salts such as the sodium or potassium salt of the copolymer.
  • salts of the copolymer may be used, however some ammonium which contain significant
  • the copolymer may be provided in the formulation in addition to a source of suitable cations where the addition of the cation source to aqueous
  • the amount of suitable cations is sufficient to provide optimum dispersant
  • the anhydride forms of the copolymer are not generally soluble in water. However, we have
  • the free acid shows a degree of solubility in water.
  • the free acid shows a degree of solubility in water.
  • formulation may contain the free acid of the copolymer (in the absence of any suitable cation
  • a cation source may be provided in a separate addition to the aqueous medium prior to the dispersing of the formulation.
  • reaction between the free acid and the cation source generates gas and the action of which facilitates the disintegration of the granule containing the insoluble material.
  • cation sources may be selected so as to
  • Cation sources suitable for inco ⁇ oration into either the formulation or the aqueous medium include sources of agriculturally acceptable cations, such as alkali metal cations.
  • the cation source is selected from the group consisting of alkaline salts such as carbonates,
  • soluble agriculturally acceptable derivatives of the copolymer include polyethyleneoxy derivatives, polyethyleneglycol derivatives, polyamide derivatives and polyvinyl alcohol
  • water-soluble it is meant that the derivatives of the copolymer are at least
  • the copolymer may inco ⁇ orate one or more first comonomers in addition to one or more
  • the polymer may also contain additional comonomer residues.
  • the copolymer may contain residues of additional ⁇ -olefin comonomers.
  • copolymers for use in the present invention also include copolymers of three or more
  • Such third comonomers which may be advantageously included in the copolymer to form a te ⁇ olymer include styrene, alphamethylstyrene, methyl methacrylate,
  • polymer backbone is provided in the presence of regularly spaced anionic charge along the polymer molecule such as is obtained by an alternating copolymer, the improved dispersant
  • repeating, units are preferably monomers but may also be dimers, trimers or small oligomers.
  • the dispersants for use in the present invention may preferably be alternating copolymers.
  • the temperature and type of solvent can influence whether an
  • the alternating, or substantially alternating character, of the copolymers is believed to be of
  • the alternating copolymer has an alternating
  • the preferred molecular weights of the copolymers are in the range of from 1000 to 90000
  • dispersants in agricultural compositions provide improved and consistent dispersant
  • alkylnaphthalene formaldehyde condensate salts alkylnaphthalene formaldehyde condensate salts.
  • copolymers is compared to that of a diisobutylene maleic anhydride sodium salt of similar
  • copolymer as herein described with other dispersants known to those skilled in the art including alkyl substituted and unsubstituted sulfonated naphthalene formaldehyde condensate salts, alkyl substituted and unsubstituted phenol formaldehyde condensate salts,
  • SC formulations are generally insoluble at ambient temperatures. Water insoluble materials
  • insecticides fungicides, biocides, molluscicides, algaicides, plant growth regulators,
  • triazine herbicides such as simazine, atrazine, terbuthylazine,
  • terbutryn terbutryn, prometryn and ametryn, urea herbicides such as diuron and fluometron, sulphonyl
  • urea herbicides such as chlorsulfuron, metsulfuron methyl, nicosulfuron and triasulfuron,
  • sulphonanilide herbicides such as flumetsulam, organophosphate insecticides such as azinphos
  • bendiocarb bendiocarb, carbaryl and BPMC, synthetic pyrethroids such as bifenthrin, as well as various types of fungicides including dimethomo ⁇ h, benomyl, carbendazim, mancozeb, triazoles
  • fertilizers and also water soluble active principles may use water dispersible formulations either by addition of inert carriers for convenience in handling or to aid in a
  • fillers and carriers for example but not limited to, natural and synthetic silicates and silicate
  • Such materials may be added as porous carriers, as moisture inhibition agents,
  • fillers may include natural silicates such as diatomacious earth, synthetic precipitated silicas, clays such as kaolin, attapulgites and
  • hydroxides or organic materials such as bagasse, charcoal, or synthetic organic polymers.
  • formulations is a surfactant wetting agent.
  • formulations is to aid removal of air from particle surfaces during manufacture and to aid
  • the role of the wetter may be to aid
  • the dispersant may itself function as a suitable wetting agent
  • At least one surfactant wetting agent may be selected
  • an alkylpolysaccharide from the group consisting of an alkylpolysaccharide; di or mono alkyl sulphosuccinate derivative; a nonionic surfactant loaded onto an inert silicate carrier; and a non-ionic
  • surfactant delivered in the form of a urea surfactant complex is delivered in the form of a urea surfactant complex.
  • the step of dispersing the formulation in an aqueous medium may be achieved by any one of the following steps:
  • dispersion of the formulation in an aqueous solution may be conducted either by hand or with
  • Mechanical agitation may include stirring, mixing,
  • the suspension of insoluble material in aqueous medium will be typically used for the
  • suspension onto the substrate may be achieved by any convenient means, including spraying,
  • Granules are generally dispersed in water prior to being sprayed by the farmer.
  • Farm sprays may be as a small back-pack handspray or a large boom spray or other
  • Formulations of the present invention may also be applied to the substrate directly, prior to dispersion.
  • the subsequent application of rain or other aqueous media is sufficient for the formulation of the suspension of particulate material.
  • formulations provide a stable aqueous dispersion of finely milled insoluble hydrophobic
  • dispersion can be measured by means of a suspensibility test as described by the CIPAC test
  • Another measure of the stability of the dispersion is the degree to which particles remain non
  • the degree to which particles may be aggregated is often measured by a wet
  • WP formulations are produced by milling the active principle either alone or in combination with fillers, dispersants and/or surfactant wetters to a suitable particle size
  • the milled material is then dry blended with a surfactant
  • a formulation will desirably have a wettability of less than 1 minute and a
  • fillers typically of particle size 5 to 15 ⁇ m, may be mixed with one or more surfactant wetters and one or more dispersants. Typically an excess of water is added to bind the particles together into agglomerates. The excess water is later reduced by suitable air drying
  • the agglomerates are typically granulated using one of many techniques including pan
  • the wetter and dispersant may either be powder blended with the active ingredient or
  • active ingredient fillers, wetter and dispersant may also be milled together in one operation prior to the addition of water.
  • a dispersion time of less than one minute is desirable, 20 seconds is excellent and 2 minutes is poor.
  • Desirably the granules should also have good suspensibility. Suspensibility is typically tested using CIPAC MT 15.1. Above 80% is a
  • the granules should have low wet sieve retention.
  • Wet sieve retention is typically
  • a further desirable property of a WG formulation is that the granules should be non-dusty and
  • resistance may be measured by subjecting granules to a set degree of agitation and measuring
  • Storage stability may be tested by storage at 50 degrees Celsius and tested as above at 1 month and 3 month intervals to determine if any properties have changed significantly.
  • the granules should maintain these properties on storage. Su ⁇ risingly, it has
  • surfactant wetting agents selected from the classes comprising alkylpolysaccharides, dialkyl and monoalkylsulphosuccinate salts,
  • nonionic surfactants loaded onto porous silicate carriers and urea surfactant complexes of non ⁇
  • the wetting agent may be combined in such formulations at a rate in excess of 1 % w/w and preferably less than 3% w/w. Most preferred from the alklypolysaccharide
  • wetting agents are alkylpolyglucosides derived from reaction with glucose and a primary hydrocarbon alcohol. Even more preferred are the highly crystalline derivatives such
  • monoalkylsulphosuccinate class are sodium or potassium salts of
  • cyclohexyl, iso-octyl and n-octyl sulphosuccinate Most preferred from the dialkylsulphosuccinate class are sodium or potassium salts of dicyclohexyl, diisooctyl and di- n-octyl sulphosuccinates.
  • Most preferred from the class of nonionic surfactants loaded onto insoluble porous silicate carriers are ethoxylated surfactants loaded onto carriers such as
  • complexes are urea adducts of alcohol ethoxylate surfactants such as TERWET 7050 (Orica
  • a humectant may also be included.
  • a dispersion is
  • additives such as antifreeze, thickeners and antisettling agents, biocides
  • SC's generally require good viscosity and storage stability. Storage stability is usually assessed as degree of top settling or syneresis, sedimenting or "claying" which is the tendency
  • copolymers are suitable. When used alone, some dispersant copolymer derivatives give a
  • the dispersant copolymers are used
  • Example 1
  • a Simazine 900g/kg WG formulation of the following composition was prepared.
  • the dispersant used was an alkylnaphthalene formaldehyde condensate salt, SCS 2258 (ICI
  • the granules were prepared by blending the solids with approximately 15% by weight of water such as to give a plastic premix which was then extmded using a Fuji-Paudal laboratory
  • the resulting WG was tested for dispersibility by recording the time in seconds required for total disintegration under uniform agitation.
  • the suspensibility was tested according to
  • a simazine 900 g/Kg WG was prepared and tested as described in Example 1 where the
  • a Simazine 900g/kg WG formulation of the following composition was prepared :
  • the dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
  • a Simazine 900g/kg WG formulation of the following composition was prepared.
  • the dispersant used was the sodium salt of copolymer of styrene and maleic anhydride.
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • dispersant being the sodium salt of a copolymer of n-octene and maleic
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a copolymer of n-decene and maleic
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a co-polymer of
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a copolymer of
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a copolymer of d-limonene and maleic
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a co-polymer of ⁇ -pinene and maleic
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a te ⁇ olymer of dicyclopentadiene,
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a te ⁇ olymer of alternating character
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a te ⁇ olymer of alternating character
  • N-vinyl-2-pyrrolidinone maleic anhydride in the ratio 37.5:25:37.5 . Results are shown in
  • a Simazine 900g/kg WG formulation was prepared and tested in the manner described in
  • Example 4 with the dispersant being the sodium salt of a te ⁇ olymer of alternating character
  • Atrazine tech. (98% w/w) 91.8 % w/w
  • dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
  • Example 15 with the dispersant being the sodium salt of a te ⁇ olymer of dicyclopentadiene,
  • a Diuron 900g/kg WG formulation of the following composition was prepared.
  • dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
  • a Simazine 900g/kg WP formulation of the following composition was prepared by blending the following :
  • dispersant used was the sodium salt a copolymer of dicyclopentadiene and maleic anhydride and the wetter used was ATPLUS G73050 (now sold under the trade mark
  • the wettability of the WP was also measured according to CIPAC test MT 53.5.1.
  • a Simazine 900g/kg WP formulation of the following composition was prepared and tested in the manner described in Example 18 where the dispersant used was the sodium salt a
  • copolymer of dicyclopentadiene and the wetting agent was the sodium salt
  • dicyclohexylsulphosuccinate used at 1.7 %w/w.
  • the formulation was prepared in the
  • alkylpolysaccharide used at 1.7% w/w on an active strength basis. (The product is 50%
  • wetting agent used was TERIC 157 (Orica Australia Pty Ltd) a nonionic
  • Rhodopol 23 0.2 Rhodia Inc.
  • the dispersant used was the sodium salt of an alternating copolymer of dicyclopentadiene and
  • the SC was prepared by dissolving the monoethylene glycol, ATLOX
  • Rodopol 23 (Rhodia Ine) in a premix and then made up to the desired volume with the
  • the invention also includes all of the steps, features, compositions and compounds referred to

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

A method of dispersing an insoluble material in an aqueous solution comprising the following steps: (i) providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double bond and α-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an α,β-unsaturated oxyacid or anhydride; and (ii) dispersing said formulation in an aqueous medium. A method according to claim 1 wherein the alicyclic monomers having an endo-cyclic double bond are selected from the group consisting of dicyclopentadiene and dimethyldicyclopentadiene.

Description

METHOD AND COMPOSITION FOR DISPERSING AN INSOLUBLE MATERIAL IN AQUEOUS SOLUTION
The present invention relates generally to dispersants, for use in agricultural applications, in particular the present invention relates to methods for the dispersion of insoluble material with
copolymeric dispersants which dispersions are formed with improved dispersibility and show
improved suspensibility. The present invention also relates to methods of producing
dispersible formulations, the formulations per se and methods of treating substrates with
dispersions produced from such formulations.
The active principles in many agricultural applications are largely hydrophobic or water
insoluble in character and are, by necessity, often administered as finely divided solids
suspended in aqueous media. The majority of these active principles are manufactured and marketed in concentrated form, possibly with the addition of other insoluble inert fillers,
which are then diluted prior to application. For example, the active principle is typically
available in the form of a suspension concentrate (SC), wettable powder (WP) or water
dispersible granule (WG). However, due to the generally hydrophobic nature of the active
principle, the addition of a suitable dispersant is essential in order to achieve an homogenous
dispersion with a minimum of mixing, such as may be achieved readily by hand or with
minimal mechanical mixing. Furthermore, once an homogenous dispersion is achieved, the
resulting suspension must remain stable for a time sufficient, at least, to allow application by
usual means such as spraying. Any settling, agglomeration or flocculation of the finely
divided solid may lead to inconsistent and ineffective application as well as blockage of the
spraying equipment. It is therefore necessary to provide a dispersant which provides easy and homogenous dispersion and results in a suspension which maintains its stability during the
application of the aqueous dispersion.
Effective dispersants for use in these applications ideally provide a suspension with acceptable
dispersibility, suspensibility and lack of agglomeration. The Collaborative International
Pesticides Analytical Council (CIPAC Handbook Volume 1) defines methods that can be used
for determining acceptable suspensibility (MT 15.1) and degree of agglomeration (MT 59.3).
For example, in suspension concentrates so-called SC formulations, this can be achieved by
the addition of about 3-5 w/w% of a standard dispersant. Wettable powder (WP) and water
dispersible granule (WG) formulations generally require the addition of standard dispersant
in the order of 6-7 w/w% in order to achieve acceptable suspensibility and degree of
agglomeration as determined by a wet sieve retention test. (MT 59.3).
Currently used dispersants for SC formulations include ethylene oxide/propylene oxide block
copolymer surfactants based on an hydrophobic moiety plus ethyleneoxide. Also used are
ether phosphate derivatives of non-ionic surfactants, especially of tristyrylphenol ethoxylates.
Conventional anionic surfactants used include sulphonated derivatives of arylformaldehyde
condensates, polyacrylates and ligno sulfonates.
Dispersants for WP and WG formulations are usually limited by the requirement that the
dispersant be solid at ambient temperatures, be non-gelling and not dissolve the active
principle. For these reasons, conventional non-ionic surfactants are often unsuitable, and
anionic dispersants are preferred. Known effective dispersants for WP and WG formulations include sulphonated alkylnaphthalene/formaldehyde condensate salts and lignosulfonate salts.
α-Olefin-polycarboxylate copolymers are well known as dispersants in a wide range of
applications including pigment dispersion, emulsion polymerisation, cosmetics and pesticidal
compositions. As far back as 1972 the sodium salt of a maleic anhydride and diisobutylene
copolymer was given an exemption from tolerance for use in pesticide formulations by the
United States Environmental Protection Authority following a petition from Rohm and Haas
Co. FR 2545325 describes the use of ammonium and alkali metal salts of maleic anhydride-
diisobutylene copolymer in pesticide granules. Similarly, EP 201417 describes the use of
copolymers of maleic anhydride with surfactants selected from sulfates and phosphates of
ethoxylated phenol derivatives in WP and WG formulations. JP 62036302 describes
copolymers having a molecular weight range of from 5000-20000 for use with granular
agrochemical compositions. Maleic anhydride and diisobutylene copolymer derivatives are
described for use in conjunction with CaCO3 and Mg salts for SC formulations in JP 06
09,302. The use of sulfonated derivatives of copolymers of maleic anhydride in water
dispersable granules is also described in JP 58-131903.
French Patent No. 2,397,444 describes stable and concentrated dispersions of active materials
which may be prepared from non-dusting powders or granular materials. It is necessary to
separate the active material in the presence of a salt of an acidic resin, such as, for example, a copolymer of maleic anhydride and an -olefinic compound; add an organic solvent which
forms, together with the aqueous medium, a two-phase system; treat such two-phase system by adding a carrier substance thereto; and then isolate the product by a reduction in the volume of the organic phase by the addition of water, the solvent gradually transferring into
the added water.
We have now found that the use of selected copolymers provides suφrisingly improved
dispersibilty and suspensibility in agrochemical formulations, as well as a number of other
ancillary benefits which will be more fully described herein.
According to a first aspect of the present invention, there is provided a method of dispersing
an insoluble material in an aqueous solution comprising the following steps:
(i) providing a formulation comprising at least one insoluble material and at least one
dispersant comprising a water soluble agriculturally acceptable derivative of a
copolymer or an agriculturally acceptable salt thereof wherein said copolymer
comprises residues of at least one first comonomer and at least one second comonomer
wherein said first comonomer is selected from the group consisting of alicyclic
monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having
a polymerizable endo-cyclic double-bond and -olefins having at least one cyclic
substituent with the proviso that said cyclic substituent is not benzene or substituted
benzene and wherein said second comonomer is an α,β-unsaturated oxyacid or
anhydride; and
(ii) dispersing said formulation in an aqueous medium. According to a second aspect of the present invention, there is provided a method of making an agrochemical formulation comprising the steps of:
(i) combining at least one insoluble material, and at least one dispersant comprising
providing a formulation comprising at least one insoluble material and at least one
dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer
comprises residues of at least one first comonomer and at least one second comonomer
wherein said first comonomer is selected from the group consisting of alicyclic
monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having
a polymerizable endo-cyclic double-bond and -olefins having at least one cyclic
substituent with the proviso that said cyclic substituent is not benzene or substituted
benzene and wherein said second comonomer is an α,β-unsaturated oxyacid or
anhydride;
(ii) milling said combination to a particle size range in order to obtain a stable, readily -
suspendible aqueous dispersion; and
(iii) stabilising said aqueous dispersion to obtain an SC formulation suitable for dilution
in water for agricultural use;
According to a third aspect of the present invention, there is provided a method of making
an agrochemical formulation comprising the steps of: (i) combining at least one insoluble material, with at least one dispersant comprising
providing a formulation comprising at least one insoluble material and at least one
dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer
comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic
monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having
a polymerizable endo-cyclic double-bond and α-olefins having at least one cyclic
substituent with the proviso that said cyclic substituent is not benzene or substituted
benzene and wherein said second comonomer is an ,β-unsaturated oxyacid or
anhydride; and
(ii) milling said combination to a desired particle size to obtain a homogeneous wettable powder (WP) formulation.
According to a fourth aspect of the present invention, there is provided a method of making
an agrochemical formulation comprising the steps of:
(i) combining at least one insoluble material suitable for agricultural use with at least one
dispersant comprising providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally
acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group
consisting of alicyclic monomers having a polymerizable exo-cyclic double bond,
alicyclic monomers having a polymerizable endo-cyclic double-bond and -olefins
having at least one cyclic substituent with the proviso that said cyclic substituent is not
benzene or substituted benzene and wherein said second comonomer is an α,β-
unsaturated oxyacid or anhydride; and
(ii) blending said combination to obtain a homogeneous wettable powder (WP)
formulation.
According to a fifth aspect of the present invention, there is provided a method of making an
agrochemical formulation comprising the steps of:
(i) combining at least one insoluble material suitable for agricultural use with at least one dispersant comprising providing a formulation comprising at least one insoluble
material and at least one dispersant comprising a water soluble agriculturally
acceptable derivative of a copolymer or an agriculturally acceptable salt thereof
wherein said copolymer comprises residues of at least one first comonomer and at
least one second comonomer wherein said first comonomer is selected from the group
consisting of alicyclic monomers having a polymerizable exo-cyclic double bond,
alicyclic monomers having a polymerizable endo-cyclic double-bond and -olefins
having at least one cyclic substituent with the proviso that said cyclic substituent is not
benzene or substituted benzene and wherein said second comonomer is an α,β- unsaturated oxyacid or anhydride;
(ii) agglomerating said combination to form discrete granular materials; and
(iii) drying said granular materials to obtain a water dispersible granule WG formulation.
According to a sixth aspect of the present invention, there is provided a formulation produced
by the process of the second, third, fourth and fifth aspects.
According to a seventh aspect of the present invention, there is provided an agricultural
formulation comprising at least one insoluble material and at least one dispersant comprising
providing a formulation comprising at least one insoluble material and at least one dispersant
comprising a water soluble agriculturally acceptable derivative of a copolymer or an
agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least
one first comonomer and at least one second comonomer wherein said first comonomer is
selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic
double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and -
olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not
benzene or substituted benzene and wherein said second comonomer is an α,β-unsaturated oxyacid or anhydride.
According to an eighth aspect of the present invention, there is provided a method of
treatment of a substrate with an insoluble material comprising the following steps: (i) preparing a formulation comprising providing a formulation comprising at least one
insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof
wherein said copolymer comprises residues of at least one first comonomer and at
least one second comonomer wherein said first comonomer is selected from the group
consisting of alicyclic monomers having a polymerizable exo-cyclic double bond,
alicyclic monomers having a polymerizable endo-cyclic double-bond and α-olefins
having at least one cyclic substituent with the proviso that said cyclic substituent is not
benzene or substituted benzene and wherein said second comonomer is an α,β- unsaturated oxyacid or anhydride;
(ii) dispersing said formulation in an aqueous medium; and
(iii) applying the dispersed formulation to a substrate.
The first comonomer for use in the present invention may be an alicyclic monomer having
a polymerizable exo-cyclic double bond. It will be understood that by alicyclic monomer is meant an aliphatic cyclic monomer containing moieties such as a cyclic alkyl, cyclic alkenyl
or heterocyclic groups and which may comprise one or more carbocyclic or heterocyclic
rings. It will be understood that by exo-cyclic is meant an alkylidene substituted cyclic structure. Alicyclic monomers having a polymerizable exo-cyclic double bond may optionally
be substituted. The substituents are not narrowly critical and may be selected in accordance
with known substitution techniques and variations to obtain optimum dispersant properties in the copolymer. Alicyclic monomers having a polymerizable exo-cyclic double bond of the
present invention may include, for example, β-pinene, 5-ethylidene-2-norbonene. methylene cyclohexane and methylene cyclopentane. The most preferred alicyclic monomer having a
polymerizable exo-cyclic double bond for use as the first comonomer in the present invention
is β-pinene.
The first comonomer for use in the present invention may be an alicyclic monomer having
a polymerizable endo-cyclic double bond. The term alicyclic monomer is as hereinabove
defined. It will be understood that by endo-cyclic is meant the polymerizable double bond has both ends (or termini) forming part of the cyclic structure of the alicyclic monomer.
Alicyclic monomers having a polymerizable endo-cyclic double bond may optionally be
substituted. The substituents are not narrowly critical and may be selected in accordance with
known substitution techniques and variations to obtain optimum dispersant properties in the
copolymer. Alicyclic monomers having a polymerizable endocyclic double bond may
include substituted and unsubstituted norbornene, cyclopentadiene and substituted
cyclopentadienes, substituted and unsubstituted dicyclopentadienes , cyclohexenes, furans and
indenes. Most preferred of the above monomers containing an endo-cyclic double bond are
dicyclopentadiene and dimethyldicyclopentadiene.
The first comonomer for use in the present invention may be an α-olefin having at least one
cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene. It will be understood that by α-olefin is meant an olefinic compound having a terminal double bond. Suitable cyclic substituents include cyclopentane, cyclohexane, and other cylcoaliphatics, heterocyclics, hetro aromatic s and polyaromatics. Examples of suitable α-olefinic compounds include limonene and similar teφenes, vinyl cyclohexanes, vinyl
cyclohexenes, vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinyl
pyrans and, vinyl pyrrolidones. Most preferred α-olefin monomers include d-limonene, vinyl
naphthalene, vinyl pyrrolidone, allyl glycidyl ether and vinyl cyclohexene.
The second monomer for use in the present invention comprises an α,β -unsaturated oxyacid
or anhydride. α,β- oxyacids comprise a polymerizable double bond adjacent to one or more
oxy acid substituents such as carboxylic, sulphonic or phosphonic groups. Examples of said
second comonomers for use in the present invention include fumaric acid, maleic acid and
itaconic acid and their corresponding anhydrides, acrylic and methacrylic acids,
vinylphosphonic acid and ethylene sulphonic acid. The most preferred comonomer of the
second type is maleic anhydride.
The dispersants are agriculturally acceptable salts or water-soluble agriculturally acceptable
derivatives of the copolymer and are preferably readily soluble in water. Suitable salts
include alkali metal salts such as the sodium or potassium salt of the copolymer. Ammonium
salts of the copolymer may be used, however some ammonium which contain significant
levels of by-products salts appear to have some limitations on their use since they have been
found to be unsuitable in some WG formulations. While not wishing to be bound by theory, it is believed that they appear to interfere with disintegration of the granule and lead to
formation of non-dispersing aggregates. While agriculturally acceptable salts of the copolymer are generally preferred, the copolymer may be provided in the formulation in addition to a source of suitable cations where the addition of the cation source to aqueous
media solubilises the copolymer.
Preferably the amount of suitable cations is sufficient to provide optimum dispersant
characteristics in the alternating copolymer. It is generally desirable to provide an excess of
cations such that a substantial amount of the alternating copolymer forms polyanionic
polymer.
The anhydride forms of the copolymer are not generally soluble in water. However, we have
found that the free acid shows a degree of solubility in water. In one embodiment the
formulation may contain the free acid of the copolymer (in the absence of any suitable cation
source). A cation source may be provided in a separate addition to the aqueous medium prior to the dispersing of the formulation.
We have found that certain combinations of free acids of the copolymer with separate addition
of a cation source prior to dispersing the formulation are advantageous. It is believed that the
reaction between the free acid and the cation source generates gas and the action of which facilitates the disintegration of the granule containing the insoluble material. In particular,
the addition of sodium carbonate leads to the generation of carbon dioxide and results in
improved disintegration of the granule. Other cation sources may be selected so as to
generate a variety of gaseous reaction products to provide improved dispersion.
Cation sources suitable for incoφoration into either the formulation or the aqueous medium include sources of agriculturally acceptable cations, such as alkali metal cations. Preferably the cation source is selected from the group consisting of alkaline salts such as carbonates,
bicarbonates, hydroxides, phosphates, alkoxides, borates, sulphites and silicates. Other water
soluble agriculturally acceptable derivatives of the copolymer include polyethyleneoxy derivatives, polyethyleneglycol derivatives, polyamide derivatives and polyvinyl alcohol
derivatives. By water-soluble it is meant that the derivatives of the copolymer are at least
partially water-soluble at ambient temperatures. Other water-soluble derivatives of the copolymer are also useful in the present invention.
The copolymer may incoφorate one or more first comonomers in addition to one or more
of the second comonomers. The polymer may also contain additional comonomer residues.
For example, the addition of a small amount, say less than 10%, of methyl methacrylate will
not substantially change the character of the copolymer.
The copolymer may contain residues of additional α-olefin comonomers. Suitable
copolymers for use in the present invention also include copolymers of three or more
comonomers. Such third comonomers which may be advantageously included in the copolymer to form a teφolymer include styrene, alphamethylstyrene, methyl methacrylate,
methacrylic acid and acrylic acid.
It is preferable that a consistent spacing of charge is maintained on the polymer molecule.
While not wishing to be bound by theory it appears that providing a consistent hydrophobic
polymer backbone is provided in the presence of regularly spaced anionic charge along the polymer molecule such as is obtained by an alternating copolymer, the improved dispersant
performance is preserved.
Also copolymers with substantially regularly spaced anionic charges along the polymer
molecule provide advantageous dispersant performance. For example the alternating, or
repeating, units are preferably monomers but may also be dimers, trimers or small oligomers.
While not wishing to be bound by theory, it is believed that the stiffness of the polymer
molecule is related to its performance as a dispersant. It is believed that improved dispersant
performance is related to the degree of steric hindrance and the resistance of the copolymer
to free rotation.
The dispersants for use in the present invention may preferably be alternating copolymers.
It will be understood by those skilled in the art that alternating copolymers may be prepared
by the careful selection of comonomers and reaction conditions. As is well known in the art,
often additional polymerization conditions should be observed in order to obtain an alternating
copolymer. For example the temperature and type of solvent can influence whether an
alternating or other type of copolymer is formed. Methods for making alternating copolymers
from the monomers as herein described will be well known to those skilled in the art of polymer synthesis.
The alternating, or substantially alternating character, of the copolymers is believed to be of
advantage in the practice of the present invention. The person skilled in the art will understand the degree of regularity necessary in order for a copolymer to be considered of
alternating character. It is preferred that the alternating copolymer has an alternating
character defined by greater than 70% of consecutive comonomer residue units being alternate
between residues of the first comonomer and the second comonomer, more preferably greater
than 90%. A high degree of control in the synthesis of such copolymers is required in most
cases to achieve this.
The preferred molecular weights of the copolymers are in the range of from 1000 to 90000
daltons. We have found that certain higher molecular weight copolymers show a certain
degree of intractability in solution and our more preferred range is from 1000-30000 daltons,
even more preferred is 1000-10000 daltons.
We have found that agriculturally acceptable salts of copolymers as described herein for use
as dispersants in agricultural compositions provide improved and consistent dispersant
performance when compared to conventionally used dispersants such as sulfonated
alkylnaphthalene formaldehyde condensate salts.
It is suφrising that agriculturally acceptable salts of copolymers as described herein give
enhanced performance when compared to previously described dispersants structures in the
prior art such as for example diisobutylene, isobutylene and styrene copolymers with maleic anhydride while still other derivatives described in those same publications, cannot be
reasonably used as dispersants in agricultural applications at all. For example we have found
that some styrene-maleic anhydride copolymer derivatives resulted in a less stable and sometimes unstable dispersion. Similarly some linear α-olefin maleic anhydride derivatives
such as those derived from n-octene and n-decene also yielded unstable dispersions affording poor suspensibility.
The performance of the agriculturally acceptable salts of copolymers described herein has
been observed at different dispersant concentrations in WP and WG formulations to exhibit
improved storage stability. Also we have found that it is possible to lower the dispersant
concentration and retain an acceptable suspensibility result, thereby achieving more efficient
is the surface coverage of the dispersant. In practical terms this means the dispersant will be
more cost effective to the end user. When the use rate of agriculturally acceptable salts of
copolymers is compared to that of a diisobutylene maleic anhydride sodium salt of similar
molecular weight typically we have found that the agriculturally acceptable salts of copolymers of this invention may give acceptable stability at a concentration significantly
lower than the corresponding diisobutylene derivative. In addition the formulations typically
show improved dispersibility. When compared to sulfonated alkyl napthelene formaldehyde
condensates, suspensibility is significantly improved, even at lower concentrations.
Methods for making such copolymers from first and second comonomers will be well known
to those skilled in the art of polymer synthesis.
The dispersant system used in embodiments of the present invention may be a mixture of the
copolymer as herein described with other dispersants known to those skilled in the art, including alkyl substituted and unsubstituted sulfonated naphthalene formaldehyde condensate salts, alkyl substituted and unsubstituted phenol formaldehyde condensate salts,
lignosulphonate salts, polyacrylate salts, and other α-olefinic unsaturated dicarboxylic acid
copolymer derivatives.
In agrochemical applications, a wide variety of insoluble materials such as active principals
are delivered in aqueous suspension. Active principals such as those used in WP, WG and
SC formulations are generally insoluble at ambient temperatures. Water insoluble materials
which may advantageously be used in WP, WG and SC formulations include herbicides,
insecticides, fungicides, biocides, molluscicides, algaicides, plant growth regulators,
anthelmintics, rodenticides, nematocides, acaricides, amoebicides, protozoacides, crop
safeners and adjuvants. Examples of such actives commonly granulated or made as powders
in agriculture include: triazine herbicides such as simazine, atrazine, terbuthylazine,
terbutryn, prometryn and ametryn, urea herbicides such as diuron and fluometron, sulphonyl
urea herbicides such as chlorsulfuron, metsulfuron methyl, nicosulfuron and triasulfuron,
sulphonanilide herbicides such as flumetsulam, organophosphate insecticides such as azinphos
methyl, chloφyrifos, sulprofos and azamethiphos, carbamate insecticides such as aldicarb,
bendiocarb, carbaryl and BPMC, synthetic pyrethroids such as bifenthrin, as well as various types of fungicides including dimethomoφh, benomyl, carbendazim, mancozeb, triazoles
such as hexaconazole and diniconazole, acaricides such as propargite. A list of such products
can be drawn from the Pesticide Dictionary (contained in the Farm Chemicals Handbook) or
the British Crop Protection Society: Pesticides Manual.
In addition, some fertilizers and also water soluble active principles may use water dispersible formulations either by addition of inert carriers for convenience in handling or to aid in a
controlled release formulation.
A wide variety of other insoluble materials are used in agricultural applications including
fillers and carriers, for example but not limited to, natural and synthetic silicates and silicate
minerals, mineral oxides and hydroxides and also natural and synthetically derived organic
materials. Such materials may be added as porous carriers, as moisture inhibition agents,
to aid binding or agglomeration properties of a formulation or simply to fill a formulation to
a convenient weight. Examples of such fillers may include natural silicates such as diatomacious earth, synthetic precipitated silicas, clays such as kaolin, attapulgites and
bentonites, zeolites, titanium dioxide, iron oxides and hydroxides, aluminium oxides and
hydroxides, or organic materials such as bagasse, charcoal, or synthetic organic polymers.
These other insoluble materials may be readily dispersed in accordance with the present invention.
An additional agent conventionally used in combination with dispersants used in the above
formulations is a surfactant wetting agent. The role of the wetting agent in the case of SC
formulations is to aid removal of air from particle surfaces during manufacture and to aid
dilution in water. In the case of WP formulations the role of the wetter may be to aid
penetration of the solids into water, while in the case of WG formulations it may aid
penetration of the granules into water and aid disintegration of granules back to primary
particle size. In some cases the dispersant may itself function as a suitable wetting agent
while in others the dispersant may show an antagonistic effect on the wetter. As a further embodiment of the present invention at least one surfactant wetting agent may be selected
from the group consisting of an alkylpolysaccharide; di or mono alkyl sulphosuccinate derivative; a nonionic surfactant loaded onto an inert silicate carrier; and a non-ionic
surfactant delivered in the form of a urea surfactant complex.
The step of dispersing the formulation in an aqueous medium may be achieved by any
convenient means dependent on the nature of the formulation. It is desirable that the
dispersion of the formulation in an aqueous solution may be conducted either by hand or with
a minimum of mechanical agitation. Mechanical agitation may include stirring, mixing,
blending and other similar processes.
The suspension of insoluble material in aqueous medium will be typically used for the
treatment of a substrate such as plant or other agricultural medium. The application of the
suspension onto the substrate may be achieved by any convenient means, including spraying,
and the like. Granules are generally dispersed in water prior to being sprayed by the farmer.
Farm sprays may be as a small back-pack handspray or a large boom spray or other
convenient means. Aerial spraying is also sometimes used.
Formulations of the present invention may also be applied to the substrate directly, prior to dispersion. The subsequent application of rain or other aqueous media is sufficient for the formulation of the suspension of particulate material.
The present invention is described with reference to WP, WG and SC formulations. In each case, formulations provide a stable aqueous dispersion of finely milled insoluble hydrophobic
particles. The stability properties of the dispersion and hence the effectiveness of the
dispersion can be measured by means of a suspensibility test as described by the CIPAC test
MT 15.1. In this test the volume fraction of suspended material is compared to that which
has settled out due to gravity after 30 minutes. Typically a dispersant achieving a reported
percentage suspersiblity about 80% would be considered as an effective dispersant for WG
and WP formulations, while in excess of 90% would be expected for an SC formulation.
Another measure of the stability of the dispersion is the degree to which particles remain non
aggregated. This may also be a property of the even distribution of the dispersant in the
formulation. The degree to which particles may be aggregated is often measured by a wet
sieve retention test as described in CIPAC test MT 59.3. In this test the dispersed solid is
poured through a series of fine sieves and retained material is measured as a fraction of the
total amount of dispersed material. Formation of such aggregates is a major problem
observed in WG formulations and to a lesser extent in WP formulations.
Generally WP formulations are produced by milling the active principle either alone or in combination with fillers, dispersants and/or surfactant wetters to a suitable particle size,
typically in the 5-15 μm range. The milled material is then dry blended with a surfactant
wetter, and/or dispersant if not already present or with additional dispersants and/or surfactant
wetters to give a homogeneous composition. The powder formulation is assessed for
wettability according to a method such as CIPAC MT 53.5.1 and suspensibility as per CIPAC MT 15.1. A formulation will desirably have a wettability of less than 1 minute and a
suspensibility above 80%. Below 60% would generally be considered unacceptable. Results which might be commercially acceptable are either determined by the local registration
authority or by the standards set by the formulators themselves.
In the case of WG formulations a suitably milled active ingredient with or without other
fillers, typically of particle size 5 to 15μm, may be mixed with one or more surfactant wetters and one or more dispersants. Typically an excess of water is added to bind the particles together into agglomerates. The excess water is later reduced by suitable air drying
techniques to an optimal level.
The agglomerates are typically granulated using one of many techniques including pan
granulation, drum granulation, fluid bed granulation, spray drying, tabletting or extrusion
techniques which are well known to those skilled in the art.
The wetter and dispersant may either be powder blended with the active ingredient or
alternatively blended as an aqueous solution in the water used to aid agglomeration. The
active ingredient, fillers, wetter and dispersant may also be milled together in one operation prior to the addition of water.
For a WG formulation to be acceptable an additional requirement is that the said granules
should readily disperse in water back to the primary dispersed particle size within a short
period. This property is known as dispersibility and in describing the current invention it is measured as the time taken for granules to disperse back to primary particle size in water
under a standard degree of agitation. A dispersion time of less than one minute is desirable, 20 seconds is excellent and 2 minutes is poor. Desirably the granules should also have good suspensibility. Suspensibility is typically tested using CIPAC MT 15.1. Above 80% is a
desirable result, less than 60% is generally regarded as undesirable. In many cases when testing granules a so-called maximum surface coverage result is often obtained. This is where
the suspensibility results reach a maximum level then plateau. Adding more dispersant will
not generally improve the result. This phenomenon is thought to be due to the particle size
distribution of the material. Usually there is a given number of particles which are of such
a size that they will settle regardless of type and concentration of dispersant.
Desirably the granules should have low wet sieve retention. Wet sieve retention is typically
tested using CIPAC MT 59.3. For the 150 μm sieve less than 0.1 % retained material is
desirable. Less than 0.02% is more desirable. Likewise for the 53 μm sieve less than 0.6% is desirable, anything less than this is more desirable.
A further desirable property of a WG formulation is that the granules should be non-dusty and
resistant to attrition. This is often a property of the method of granulation used and the level
of compaction there obtained. Often there is an observed tradeoff between the dispersibility properties of a WG formulation and the level of compaction and attrition resistance. Attrition
resistance may be measured by subjecting granules to a set degree of agitation and measuring
the level of smaller particles generated by means of passing through sieves of various sizes.
Storage stability may be tested by storage at 50 degrees Celsius and tested as above at 1 month and 3 month intervals to determine if any properties have changed significantly. Preferably, the granules should maintain these properties on storage. Suφrisingly, it has
been observed that, upon prolonged storage, solid formulations such as WP and WG
formulations containing dispersants such as those described herein are not as susceptible to
deterioration in dispersability and suspensibility as formulations of the prior art. Further it
is observed that WG formulations prepared containing dispersants such as those described
herein which are prepared by methods, such as extrusion, leading to a high degree of
compaction to afford attrition resistance, will still show ready dispersibility.
We have also found that WP and WG formulations which incoφorate the dispersants
described herein require typically less dispersant, than for presently known WP and WG
formulations.
As a further embodiment of the present invention in the case of WP and WG formulations the
dispersants herein described may be combined with surfactant wetting agents selected from the classes comprising alkylpolysaccharides, dialkyl and monoalkylsulphosuccinate salts,
nonionic surfactants loaded onto porous silicate carriers and urea surfactant complexes of non¬
ionic surfactants. The wetting agent may be combined in such formulations at a rate in excess of 1 % w/w and preferably less than 3% w/w. Most preferred from the alklypolysaccharide
class of wetting agents are alkylpolyglucosides derived from reaction with glucose and a primary hydrocarbon alcohol. Even more preferred are the highly crystalline derivatives such
as obtained from ECOTERIC AS 20 and ECOTERIC AS 10 (Orica Australia Pty Ltd). Most
preferred from the monoalkylsulphosuccinate class are sodium or potassium salts of
cyclohexyl, iso-octyl and n-octyl sulphosuccinate. Most preferred from the dialkylsulphosuccinate class are sodium or potassium salts of dicyclohexyl, diisooctyl and di- n-octyl sulphosuccinates. Most preferred from the class of nonionic surfactants loaded onto insoluble porous silicate carriers are ethoxylated surfactants loaded onto carriers such as
TERIC 157 (Orica Australia Pty Ltd). Most preferred wetting agents from the urea surfactant
complexes are urea adducts of alcohol ethoxylate surfactants such as TERWET 7050 (Orica
Australia Pty Ltd). The wetters herein described show good wettability and dispersibility for
the formulations and have the additional advantage of showing storage stability in
combination with the copolymer dispersants described. Whereas by comparison some
commonly used WG and WP wetters such as alkylnaphthalene sulphonate salts and
lignosulphonate salts have been found to show poor storage stability.
In the case of SC formulations in the present invention an active ingredient is typically added
to water containing a dispersant, preferably with a surfactant wetting agent together with a
conventional non-ionic dispersant. A humectant may also be included. A dispersion is
formed using high shear mixing. The dispersion is then milled by any one of several means
of wet milling so that the mean particle size of the dispersed solid is below 5 μm more
typically in the range of from 1 to 3μm. The resulting product is known as a millbase and
may be modified with additives such as antifreeze, thickeners and antisettling agents, biocides
and colouring agents may be added. For an SC formulation to be acceptable it should not
show a high degree of thickening, settling or growth of aggregates over time. These physical
properties can be assessed by visual observation.
SC's generally require good viscosity and storage stability. Storage stability is usually assessed as degree of top settling or syneresis, sedimenting or "claying" which is the tendency
to form a sticky layer on the bottom and "bleeding" which is the tendency of the dispersion
to separate without necessarily displaying even settling. Redispersibility is also important.
These may also be assessed visually.
For SC formulations in the case of dispersants described herein only certain dispersant
copolymers are suitable. When used alone, some dispersant copolymer derivatives give a
viscosity of slurry premix unsuitable for milling so it is preferable to combine the dispersant
with another fast acting well known dispersant such as an EO/PO block co-polymer type
dispersant. While not wishing to be bound by theory it appears that the dispersant needs time
to migrate to the surface of the dispersed particles. The dispersant copolymers are used
synergistically with other known dispersants in some cases.
While the present invention has been described with reference to agrochemical formulations,
it will be apparent that the improvements in dispersibility and suspensibility will render the
present invention useful in other applications. The present invention will now be further
described with reference to the following non-limiting examples and figures. All percentages
recited herein are by weight of the total composition unless otherwise specified. Example 1.
A Simazine 900g/kg WG formulation of the following composition was prepared.
Simazine tech. (98% w/w) 91.8 % w/w
MORWET EFW 1.5 (Witco Coφ.)
DISPERSANT 6.2
Water 0.5%
The dispersant used was an alkylnaphthalene formaldehyde condensate salt, SCS 2258 (ICI
Surfactants).
The granules were prepared by blending the solids with approximately 15% by weight of water such as to give a plastic premix which was then extmded using a Fuji-Paudal laboratory
scale extrusion granulator. The resulting granules were then dried by means of a fluid bed
drier back to a water content of approximately 0.5% w/w.
The resulting WG was tested for dispersibility by recording the time in seconds required for total disintegration under uniform agitation. The suspensibility was tested according to
CIPAC MT 15.1 and the wet sieve retention was tested using 150μm and 53μm sieves
according to CIPAC MT 59.3. Results are recorded in TABLE 1.
Example 2
A simazine 900 g/Kg WG was prepared and tested as described in Example 1 where the
dispersant used was POLYFON H (Westvaco Coφ), a lignosulphonate salt. The results are
described in TABLE 1. Example 3.
A Simazine 900g/kg WG formulation of the following composition was prepared :
Simazine tech. (98% w/w) 91.8 % w/w
ATPLUS G73050 1.5
(now sold under the trade mark TERSPERSE 7050, Orica Australia Pty Ltd)
DISPERSANT 3.1
Kaolin 3.1
Water 0.5%
The dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
anhydride of approximate molecular weight 1,000 to 3,000. The granules were prepared and
tested in the manner described in Example 1. The results are shown in TABLE 1.
Example 4.
A Simazine 900g/kg WG formulation of the following composition was prepared.
Simazine tech. (98% w/w) 91.8 % w/w
ATPLUS G73050 1.5
(now sold under the trade mark TERSPERSE 7050, Orica Australia Pty Ltd)
DISPERSANT 3.1
Kaolin 3.1
Water 0.5%
The dispersant used was the sodium salt of copolymer of styrene and maleic anhydride. The
granules were prepared and tested in the manner described in Example 1. Results are shown in TABLE T
Example 5.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
example 4 with the dispersant being the sodium salt of a copolymer of n-octene and maleic
anhydride of approximate molecular weight 13000. Results are shown in TABLE 1.
Example 6.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a copolymer of n-decene and maleic
anhydride of approximate molecular weight 15000. Results are shown in TABLE 1.
Example 7.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a co-polymer of
dimethyldicyclopentadiene and a methyl ester derived from maleic anhydride. Results are
shown in TABLE 1.
Example 8.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a copolymer of
dimethyldicyclopentadiene and maleic anhydride. Results are shown in TABLE 1. Example 9.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a copolymer of d-limonene and maleic
anhydride. Results are shown in TABLE 1.
Example 10
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a co-polymer of β-pinene and maleic
anhydride. Results are shown in TABLE 1.
Example 11.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a teφolymer of dicyclopentadiene,
alphamethylstyrene and maleic anhydride. Results are shown in TABLE 1.
Example 12.
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a teφolymer of alternating character
between monomers of first and second type comprising alphamethyl styrene : 4-vinylpyridine
: maleic anhydride in the molar ratio 37.5:25:37.5 . Results are shown in TABLE 1.
Example 13
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in Example 4 with the dispersant being the sodium salt of a teφolymer of alternating character
between monomers of first and second type comprising alphamethyl styrene :
N-vinyl-2-pyrrolidinone : maleic anhydride in the ratio 37.5:25:37.5 . Results are shown in
TABLE 1
Example 14
A Simazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 4 with the dispersant being the sodium salt of a teφolymer of alternating character
between monomers of first and second type comprising alphamethyl styrene :
1-vinylimidazole : maleic anhydride in the mole ratio 48:4:48 . Results are shown in TABLE
1
Example 15
An Atrazine 900g/kg WG formulation of the following composition was prepared.
Atrazine tech. (98% w/w) 91.8 % w/w
ATPLUS G73050 1.5
(now sold under the trade mark TERSPERSE 7050, Orica Australia Pty Ltd)
DISPERSANT 3.1
Kaolin 3.1
Water 0.5
where the dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
anhydride. The granules were made and tested as described in Example 1. Results are shown
in TABLE 1. Example 16.
An Atrazine 900g/kg WG formulation was prepared and tested in the manner described in
Example 15 with the dispersant being the sodium salt of a teφolymer of dicyclopentadiene,
alphamethylstyrene and maleic anhydride. Results are shown in TABLE 1.
Example 17.
A Diuron 900g/kg WG formulation of the following composition was prepared.
Diuron tech. (97% w/w) 92.8 % w/w
ATPLUS G73050 1.5 (now sold under the trade mark TERSPERSE 7050, Orica Australia Pty Ltd)
DISPERSANT 3.1
Kaolin 2.1
Water 0.5
where the dispersant used was the sodium salt of a copolymer of dicyclopentadiene and maleic
anhydride. The granules were made and tested as described in Example 1. Results are shown in TABLE T
Example 18.
A Simazine 900g/kg WP formulation of the following composition was prepared by blending the following :
Simazine tech. (98% w/w) 91.8 % w/w
WETTER 1.7
DISPERSANT 3.1 Kaolin 3.4
Where the dispersant used was the sodium salt a copolymer of dicyclopentadiene and maleic anhydride and the wetter used was ATPLUS G73050 (now sold under the trade mark
TERSPERSE 7050, Orica Australia Pty Ltd). Results for suspensibility are shown in TABLE
2. The wettability of the WP was also measured according to CIPAC test MT 53.5.1.
Example 19.
A Simazine 900g/kg WP formulation of the following composition was prepared and tested in the manner described in Example 18 where the dispersant used was the sodium salt a
copolymer of dicyclopentadiene and the wetting agent was the sodium salt
dicyclohexylsulphosuccinate used at 1.7 %w/w. The formulation was prepared in the
manner described in Example 1. Results are shown in TABLE 2.
Example 20.
A Simazine 900 g/Kg WP formulation was prepared and tested as described in Example 18
excepting that the wetting agent used was ECOTERIC AS 20 (Orica Australia Pty Ltd), an
alkylpolysaccharide used at 1.7% w/w on an active strength basis. (The product is 50%
strength in water). The results are shown in TABLE 2.
Example 21.
A Simazine 900 g/Kg WP formulation was prepared and tested as described in Example 18
excepting that the wetting agent used was TERIC 157 (Orica Australia Pty Ltd) a nonionic
wetter loaded onto an insoluble porous carrier used at 1.7% w/w. The results are shown in TABLE 2.
Example 22.
An Atrazine 900g/Kg SC formulation of the following composition was prepared.
Atrazine tech. 97% w/w 51.5 % w/v
Monoethylene glycol 4.0 ATLOX 4896A 2
(Now sold under the trade mark TERSPERSE 4896,Orica Australia Pty Ltd)
DISPERSANT 2
Silicone antifoam 0.2
Rhodopol 23 0.2 (Rhodia Inc.)
Proxel GXL 20 0.1 (Zeneca pic)
Water 55.0
The dispersant used was the sodium salt of an alternating copolymer of dicyclopentadiene and
maleic anhydride. The SC was prepared by dissolving the monoethylene glycol, ATLOX
4896A (now sold under the trade mark of TERSPERSE 4896, Orica Australia Pty Ltd) and
DISPERSANT in 85% of the water and adding the Atrazine tech. and antifoam with vigorous
mixing to form a slurry or millbase premix. The premix is then milled using a Dynomill
laboratory scale bead mill to give a suitable particle size distribution of > 98 % of particles
below 5μm. The millbase thus obtained was then blended with Proxel GXL 20 (Zeneca pic)
and Rodopol 23 (Rhodia Ine) in a premix and then made up to the desired volume with the
remaining water and mixed to a homogeneous mixture. The SC thus obtained was of
usable viscosity and was found to be storage stable after storage at 2 degrees C and 50 degrees C for one month, with minimal syneresis and thickening and no claying,
sedimentation or aggregates being observed. Example 23.
It was attempted to make an SC formulation according to the formula of Example 22 with 4 % w/w of the sodium salt of an alternating copolymer of dicyclopentadiene and maleic
anhydride and only 0.5% w/w ATLOX 4896A (now sold under the trade mark of TERSPERSE 4896, Orica Australia Pty Ltd) being used. The resulting millbase premix was
of a viscosity which would not allow it to be milled.
TABLE 1
WG Test Results
Figure imgf000038_0001
Figure imgf000039_0001
- not tested T0 initial result
* unavailable to date T, after 1 monthstorage at 50°C
T, after 3 months storage at 50°
TABLE 2 WP Test Results
Figure imgf000040_0002
Figure imgf000040_0001
Those skilled in the art will appreciate that the invention described herein is susceptible to
variations and modifications other than those specifically described. It is to be understood that
the invention includes all such variations and modifications which fall within its spirit and scope.
The invention also includes all of the steps, features, compositions and compounds referred to
or indicated in this specification, individually or collectively, and any and all combinations of any two or more of said steps or features.

Claims

1. A method of dispersing an insoluble material in an aqueous solution comprising the following steps:
(i) providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓-unsaturated oxyacid or anhydride; and
(ii) dispersing said formulation in an aqueous medium.
2. A method according to claim 1 wherein the alicyclic monomers having polymerizable exo-cyclic double bond are selected from the group consisting of ╬▓-pinene, 5-ethylidene-2- norbonene, methylene cyclohexane and methylene cyclopentane.
3. A method according to claim 1 wherein the alicyclic monomers having polymerizable double bond are ╬▓-pinene.
4. A meti od according to claim 1 wherein the alicyclic monomers having an endo-cyclic double bond are selected from the group consisting of substituted and unsubstituted norbornene, cyclopentadiene and substituted cyclopentadienes, substituted and unsubstituted dicyclopentadienes, cyclohexenes, furans and indenes.
5. A method according to claim 1 wherein the alicyclic monomers having an endo-cyclic double bond are selected from the group consisting of dicyclopentadiene and dimethyldicyclopentadiene .
5 6. A method according to claim 1 wherein the α-olefins having at least one cyclic substituent are selected from the group consisting of limonene and teφenes, vinyl cyclohexanes, vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinyl pyrans and, vinyl pyrrolidones.
10 7. A method according to claim 1 wherein the ╬▒-olefins having at least one cyclic substituent are selected from the group consisting of d-limonene, vinyl naphthalene, vinyl pyrrolidone, allyl glycidyl ether and vinyl cyclohexene.
8. A method according to claim 1 wherein the second comonomer is selected from the 15 group consisting of fumaric acid, maleic acid and itaconic acid and their corresponding anhydrides, acrylic and methacrylic acids, vinylphosphonic acid and ethylene sulphonic acid.
9. A method according to claim 1 wherein the second comonomer is maleic anhydride.
20 10. A method according to claim 1 wherein the copolymer is an alternating copolymer.
11. A method according to claim 10 wherein the alternating copolymer has an alternating character defined by greater than 70% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer.
25
12. A method according to claim 10 wherein the alternating copolymer has an alternating character defined by greater than 90% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer.
30 13. A method according to claim 1 wherein the copolymer contains additional comonomer residues which will not substantially change the character of the copolymer.
14. An agricultural formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or
5 an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒- olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not 10 benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓ -unsaturated oxyacid or anhydride.
15. An agricultural formulation according to claim 14 wherein the formulation is in the form of a suspension concentrate (SC), a wettable powder (WP) or a water dispersible granule (WG).
15
16. A method according to claim 14 wherein the alicyclic monomers having polymerizable exo-cycloc double bond are selected from the group consisting of ╬▓-pinene, 5-ethylidene-2- norbonene, methylene cyclohexane and methylene cyclopentane.
20 17. A method according to claim 14 wherein the alicyclic monomers having polymerizable double bond are ╬▓-pinene.
18. A method according to claim 14 wherein the alicyclic monomers having an endo- cyclic double bond are selected from the group consisting of substituted and unsubstituted
25 norbornene, cyclopentadiene and substituted cyclopentadienes, substituted and unsubstituted dicyclopentadienes , cyclohexenes, furans and indenes.
19. A method according to claim 14 wherein the alicyclic monomers having an endo- cyclic double bond are selected from the group consisting of dicyclopentadiene and
30 dimethyldicyclopentadiene.
20. A method according to claim 14 wherein the α-olefins having at least one cyclic substituent are selected from the group consisting of limonene and teφenes, vinyl cyclohexanes, vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinyl pyrans and, vinyl pyrrolidones.
5
21. A method according to claim 14 wherein the ╬▒-olefins having at least one cyclic substituent are selected from the group consisting of d-limonene, vinyl naphthalene, vinyl pyrrolidone, allyl glycidyl ether and vinyl cyclohexene.
10 22. A method according to claim 14 wherein the second comonomer is selected from the group consisting of fumaric acid, maleic acid and itaconic acid and their corresponding anhydrides, acrylic and methacrylic acids, vinylphosphonic acid and ethylene sulphonic acid.
23. A method according to claim 14 wherein the second comonomer is maleic anhydride. 15
24. A method according to claim 14 wherein the copolymer is an alternating copolymer.
25. A method according to claim 24 wherein the alternating copolymer has an alternating character defined by greater than 70% of consecutive comonomer residue units being alternate 0 between residues of the first comonomer and the second comonomer.
26. A method according to claim 24 wherein the alternating copolymer has an alternating character defined by greater than 90% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer, 5
27. A method according to claim 14 wherein the copolymer contains additional comonomer residues which will not substantially change the alternating character of the copolymer.
28. An agricultural formulation according to claim 14 wherein the dispersant is readily 30 soluble in water.
29. An agricultural formulation according to claim 14 wherein the dispersant is an agriculturally acceptable salt of the copolymer and wherein the salt comprises sodium, potassium and/or ammonium ions.
5 30. An agricultural formulation according to claim 14 wherein the copolymer is polyanionic.
31. An agricultural formulation according to claim 14 wherein the copolymer is in the form of its free acid.
10 32. An agricultural formulation according to claim 14 wherein the dispersant is a water- soluble agriculturally acceptable derivative of the copolymer wherein said derivative is selected from the group consisting of polyalkyleneoxy derivatives, polyethyleneglycol derivatives, polyamide derivatives and polyvinyl alcohol derivatives.
15 33. An agricultural formulation according to claim 14 wherein copolymers are in the range of from 1000 to 90000 daltons.
34. An agricultural formulation according to claim 14 wherein copolymers are in the range of from 1 ,000 to 30,000 daltons. 0
35. An agricultural formulation according to claim 4 wherein alternating copolymers are in the range of from 1000 to 10000 daltons.
36. An agricultural formulation according to claim 14 wherein the water-insoluble materials 25 are selected from the group consisting of herbicides, insecticides, fungicides, biocides, molluscicides, algaicides, plant growth regulators, anthelmintics, rodenticides, nematocides, acaricides, amoebicides, protozoacides, fertilizers, crop safeners fillers and carriers and other adjuvants.
30 37. An agricultural formulation according to claim 14 wherein the formulation further comprises a surfactant wetting agent.
38. A method of making an agrochemical formulation comprising the steps of:
(i) providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓ -unsaturated oxyacid or anhydride;
39. A method according to claim 38 comprising the steps of:
(i) combining at least one insoluble material, and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo- cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double- bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓ -unsaturated oxyacid or anhydride;
(ii) milling said combination to a particle size range in order to obtain a stable, readily - suspendible aqueous dispersion; and
(iii) stabilising said aqueous dispersion to obtain an SC formulation suitable for dilution in water for agricultural use;
40. A method according to claim 38 comprising the steps of:
(i) comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo- cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double- bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓-unsaturated oxyacid or anhydride; and
(ii) milling said combination to a desired particle size to obtain a homogeneous wettable powder (WP) formulation.
41. A method according to claim 38 comprising the steps of:
(i) combining at least one insoluble material suitable for agricultural use with at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓-unsaturated oxyacid or anhydride; and
(ii) blending said combination to obtain a homogeneous wettable powder (WP) formulation.
42. A method according to claim 38 comprising the steps of:
5 (i) combining at least one insoluble material suitable for agricultural use with at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic
10 monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓-unsaturated oxyacid or anhydride;
15
(ii) agglomerating said combination to form discrete granular materials; and
(iii) drying said granular materials to obtain a water dispersible granule WG formulation.
20 43. A method according to claim 38 wherein the alicyclic monomers having polymerizable exo-cyclic double bonds are selected from the group consisting of ╬▓-pinene, 5-ethylidene-2- norbonene, methylene cyclohexane and methylene cyclopentane.
44. A method according to claim 38 wherein the alicyclic monomer having a 25 polymerizable double bond is ╬▓-pinene.
45. A method according to claim 38 wherein the alicyclic monomers having an endo- cyclic double bond are selected from the group consisting of substituted and unsubstituted norbornene, cyclopentadiene and substituted cyclopentadienes, substituted and unsubstituted
30 dicyclopentadienes , cyclohexenes, furans and indenes.
46. A method according to claim 38 wherein the alicyclic monomers having an endo- cyclic double bond are selected from the group consisting of dicyclopentadiene and dimethyldicyclopentadiene.
5 47. A method according to claim 38 wherein the α-olefin having at least one cyclic substituent are selected from the group consisting of limonene and teφenes, vinyl cyclohexanes, vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinyl pyrans and, vinyl pyrrolidones.
10 48. A method according to claim 38 wherein the ╬▒-olefin having at least one cyclic substituent are selected from the group consisting of d-limonene, vinyl naphthalene, vinyl pyrrolidone, allyl glycidyl ether and vinyl cyclohexene.
49. A method according to claim 38 wherein the second comonomer is selected from the 15 group consisting of fumaric acid, maleic acid and itaconic acid and their corresponding anhydrides, acrylic and methacrylic acids, vinylphosphonic acid and ethylene sulphonic acid.
50. A method according to claim 38 wherein the second comonomer is maleic anhydride.
20 51. A method according to claim 38 wherein the copolymer is an alternating copolymer.
52. A method according to claim 51 wherein the alternating copolymer has an alternating character defined by greater than 70% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer.
25
53. A method according to claim 51 wherein the alternating copolymer has an alternating character defined by greater than 90% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer,
30 54. A method according to claim 38 wherein the copolymer contains additional comonomer residues which will not substantially change the character of the copolymer.
55. An agricultural formulation according to claim 38 wherein the dispersant is readily soluble in water.
5
56. An agricultural formulation according to claim 38 wherein the dispersant is an agriculturally acceptable salt of the copolymer and wherein the salt comprises sodium, potassium and/or ammonium ions.
10 57. An agricultural formulation according to claim 38 wherein the copolymer is polyanionic.
58. An agricultural formulation according to claim 38 wherein the copolymer is in the form of its free acid.
15 59. An agricultural formulation according to claim 38 wherein the dispersant is a water- soluble agriculturally acceptable derivative of the copolymer wherein said derivative is selected from the group consisting of polyalkleneoxy derivatives, polyethyleneglycol derivatives, polyamide derivatives and polyvinyl alcohol derivatives.
20 60. An agricultural formulation according to claim 38 wherein copolymers are in the range of from 1000 to 90000 daltons.
61. An agricultural formulation according to claim 38 wherein copolymers are in the range of from 1000 to 30000 daltons.
25
62. An agricultural formulation according to claim 38 wherein copolymers are in the range of from 10,000 to 30,000 daltons.
63. An agricultural formulation according to claim 38 wherein the water-insoluble materials 30 are selected from the group consisting of herbicides, insecticides, fungicides, biocides, molluscicides, algaicides, plant growth regulators, anthelmintics, rodenticides, nematocides, acaricides, amoebicides, protozoacides, fertilizers, crop safeners fillers and carriers and other adjuvants.
64. An agricultural formulation according to claim 38 wherein the formulation further 5 comprises a surfactant wetting agent.
65. A method according to any one of claims 40 to 42 wherein said dispersant achieves a percentage suspensibility of greater than 80%.
10 66. A method according to claim 39 wherein said dispersant achieves a percentage suspensibility of greater than 90%.
67. A method according to either claim 40 or claim 41 wherein the milling step produces a mean particle size in the range of from 5 to 15╬╝m.
15
68. A method according to claim 67 wherein the wettable powder has a wettability of less than 1 minute and a suspensibility above 80%.
69. A method according to claim 42 wherein the milling step produces a mean particle size 20 in the range of from 5 to 15╬╝m.
70. A method according to claim 42 wherein the formulation has a dispersion time of less than 1 minute.
25 71. A method according to claim 42 wherein the formulation has a dispersion time of less than 20 seconds.
72. A method according to claim 42 wherein the formulation has a suspensibility of above 80%.
30
73. A method according to claim 42 wherein the formulation has a wet sieve retention. For a 150 ╬╝m sieve is less than 0.1 % retained material and is for a 53 ╬╝m sieve is less than 0.6% .
74. A method according to claim 39 wherein the milling step produces a mean particle size ofless tha 5╬╝m.
75. A method according to claim 39 wherein the milling step produces a mean particle size in the range of from 1 to 3 ╬╝m.
76. An agricultural formulation produced by the method of any one of claims 39 to 42.
77. a method of treatment of a substrate with an insoluble material comprising the following steps:
(i) preparing a formulation comprising providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of a copolymer or an agriculturally acceptable salt thereof wherein said copolymer comprises residues of at least one first comonomer and at least one second comonomer wherein said first comonomer is selected from the group consisting of alicyclic monomers having a polymerizable exo-cyclic double bond, alicyclic monomers having a polymerizable endo-cyclic double-bond and ╬▒-olefins having at least one cyclic substituent with the proviso that said cyclic substituent is not benzene or substituted benzene and wherein said second comonomer is an ╬▒,╬▓- unsaturated oxyacid or anhydride;
(ii) dispersing said formulation in an aqueous medium; and
(iii) applying the dispersed formulation to a substrate.
78. A method according to claim 77 wherein the alicyclic monomers having polymerizable exo-cyclic double bond are selected from the group consisting of ╬▓-pinene, 5-ethylidene-2- norbonene, methylene cyclohexane and methylene cyclopentane.
79. A method according to claim 77 wherein the alicyclic monomers having polymerizable double bond are ╬▓-pinene.
80. A method according to claim 77 wherein the alicyclic monomers having an endo- 5 cyclic double bond are selected from the group consisting of substituted and unsubstituted norbornene, cyclopentadiene and substituted cyclopentadienes, substituted and unsubstituted dicyclopentadienes , cyclohexenes, furans and indenes.
81. A method according to claim 77 wherein the alicyclic monomers having an endo- 10 cyclic double bond are selected from the group consisting of dicyclopentadiene and dimethyldicyclopentadiene .
82. A method according to claim 77 wherein the α-olefins having at least one cyclic substituent are selected from the group consisting of limonene and teφenes, vinyl
15 cyclohexanes, vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinyl pyrans and, vinyl pyrrolidones.
83. A method according to claim 77 wherein the ╬▒-olefins having at least one cyclic substituent are selected from the group consisting of d-limonene, vinyl naphthalene, vinyl
20 pyrrolidone, allyl glycidyl ether and vinyl cyclohexene.
84. A method according to claim 77 wherein the second comonomer is selected from the group consisting of fumaric acid, maleic acid and itaconic acid and their corresponding anhydrides, acrylic and methacrylic acids, vinylphosphonic acid and ethylene sulphonic acid.
25
85. A method according to claim 77 wherein the second comonomer is maleic anhydride.
86. A method according to claim 77 wherein the copolymer is an alternating copolymer.
30 87. A method according to claim 86 wherein the alternating copolymer has an alternating character defined by greater than 70% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer.
88. A method according to claim 86 wherein the alternating copolymer has an alternating 5 character defined by greater than 90% of consecutive comonomer residue units being alternate between residues of the first comonomer and the second comonomer,
89. A method according to claim 77 wherein the copolymer contains additional comonomer residues which will not substantially change the character of the copolymer.
10
90. An agricultural formulation according to claim 77 wherein the dispersant is readily soluble in water.
91. An agricultural formulation according to claim 77 wherein the dispersant is an 15 agriculturally acceptable salt of the copolymer and wherein the salt comprises sodium, potassium and/or ammonium ions.
92. An agricultural formulation according to claim 77 wherein the copolymer is polyanionic.
20 93. An agricultural formulation according to claim 77 wherein the copolymer is in the form of its free acid.
94. An agricultural formulation according to claim 77 wherein the dispersant is a water- soluble agriculturally acceptable derivative of the copolymer wherein said derivative is selected
25 from the group consisting of polyalkyleneoxy derivatives, polyethyleneglycol derivatives, polyamide derivatives and polyvinyl alcohol derivatives.
95. An agricultural formulation according to claim 77 wherein copolymers are in the range of from 1000 to 90000 daltons.
30
96. An agricultural formulation according to claim 77 wherein copolymers are in the range of from 1000 to 30000 daltons.
97. An agricultural formulation according to claim 77 wherein copolymers are in the range of from 1000 to 10000 daltons.
98. An agricultural formulation according to claim 77 wherein the water-insoluble materials are selected from the group consisting of herbicides, insecticides, fungicides, biocides, moUuscicides, algaicides, plant growth regulators, anthelmintics, rodenticides, nematocides, acaricides, amoebicides, protozoacides, fertilizers, crop safeners fillers and carriers and other adjuvants.
99. An agricultural formulation according to claim 77 wherein the formulation further comprises a surfactant wetting agent.
PCT/AU1998/000853 1997-10-14 1998-10-14 Method and composition for dispersing an insoluble material in aqueous solution WO1999018786A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484152A1 (en) * 1990-11-01 1992-05-06 Nippon Shokubai Co., Ltd. Additive composition for coal-water slurry and coal-water slurry composition

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Publication number Priority date Publication date Assignee Title
EP0484152A1 (en) * 1990-11-01 1992-05-06 Nippon Shokubai Co., Ltd. Additive composition for coal-water slurry and coal-water slurry composition

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