WO2006080917A1

WO2006080917A1 - Surface-active polymers - agricultural applications

Info

Publication number: WO2006080917A1
Application number: PCT/US2005/002491
Authority: WO
Inventors: Alan J. Stern; Duy T. Nguyen; George A. Smith; Katie R. HAND; Samir S. Ashrawi
Original assignee: Huntsman Petrochemical Corporation
Priority date: 2005-01-25
Filing date: 2005-01-25
Publication date: 2006-08-03

Abstract

This invention relates generally to agricultural formulations, and more particularly to formulations useful in agrucultural applications which contain anionic water-soluble polymers having surface active properties. Compositions according to the invention are highly effective dispersants for the preparation of high solids dispersions of solid agriculturally-active materials.

Description

Surface-Active Polymers - Agricultural Applications

Field of the Invention

This invention relates generally to agricultural formulations, and more particularly

to formulations useful in agricultural applications which contain anionic water-soluble

polymers having surface active properties. Compositions according to the invention are

highly effective dispersants for the preparation of high solids dispersions of solid

agriculturally-active materials.

Background Information

High solids suspensions of small particulate solids have been traditionally difficult to

achieve while maintaining a viscosity that allows pouring, pumping, and grinding to be done with ease. Thus there is a need for new, cost-effective high performance dispersants in

many industrial areas. Some fields in which high solids suspensions are used include paints

and coatings, printing inks, agricultural products, and silicon chip manufacture.

The prior art contains information on many different classes of dispersant materials.

Dispersants are typically described as surface active materials with strong affinity for solid

surfaces. They may be anionic or nonionic or even cationic or amphoteric, but all have in

common the ability to prevent the agglomeration of particles suspended in a liquid media.

Because of the different molecular structure and crystal surface properties present

among the many different materials used industrially in suspension form, no single

dispersant will be ideal for every need.

i Summary of the Invention

The present invention provides polymers having surfactant properties and useful in

agricultural end-use formulations which has the structure: '

in which X is selected from the group consisting of: oxygen and — NEl₄ — , the sum of p and

q is any value between about 0 and about 100, including 0 and 100, wherein R₁ is independently selected from the group consisting of: hydrogen, and any C₁ to C₂₀ alkyl

group; R₂ and R₃ may each be the same or different, and when the same they are selected from the group consisting of: any C₁ to C₆ alkyl group, and when R₂ and R₃ are different they

are each independently selected from the group consisting of: any C₁ to C₆ alkyl group; R₄ is

independently selected from the group consisting of: hydrogen, and any C₁ to C₆ alkyl

group; R₅ and R₆ are each independently selected from the group consisting of: H, --CN, ~ CONH₂ (amide), -COOR₇ (ester), -CO₂H, -COO ^", and

O

-C-O(R₂O)(R₃O)R₇ in which R₇ is selected from the group consisting of: hydrogen, methyl, and ethyl; and wherein n is sufficient to yield a weight average molecular weight of said polymer of any value in the range of between about 3,000 and 100,000, including salts thereof.

Brief Description of the Drawings

In the annexed drawings:

FIG. 1 shows the viscosity of a captan suspension according to the present invention, and

a captan suspension according to the prior art;

FIG. 2 shows the surface tension of a water-soluble polymer according to the present invention

as a function of its concentration in water;

FIG. 3 shows the surface tension of a water-soluble polymer according to an alternative embodiment of the present invention as a function of its concentration in water;

FIG. 4 shows the surface tension of a water-soluble polymer according to an alternative

embodiment of the present invention as a function of its concentration in water; and

FIG. 5 shows the surface tension of a water-soluble polymer according to an alternative

embodiment of the present invention as a function of its concentration in water.

Brief Description of the Drawings

In the annexed drawings:

FIG. 1 shows the viscosity of a captan suspension according to the present invention, and a captan suspension according to the prior art;

FIG. 2 shows the surface tension of a water-soluble polymer according to the present

invention

as a function of its concentration in water;

FIG. 3 shows the surface tension of a water-soluble polymer according to an alternative

embodiment of the present invention as a function of its concentration in water;

Detailed Description

The present invention concerns a new class of highly efficient dispersant, derived

from the co-polymerization of acrylate and maleamide monomers. The maleamide monomer is a derivative of maleic anhydride and a SURFONAMINE® ML-300 dispersant

(a.k.a. maleamide"), which contain both amide and carboxylic acid functional groups.

The new dispersants are useful for the preparation of high solids suspensions of

agriculturally-active materials. Using this invention, it is possible to prepare suspensions having lower viscosity than can be made when typical commercial dispersants such as

MORWET® D-425 dispersants are used. Reduced viscosity allows the manufacture of more highly concentrated suspensions, thus allowing the delivery of more active ingredient

and less diluent in each batch of product than heretofore realized.

The anionic surface active water soluble polymers of the present invention are

prepared by copolymerizing polymerizable amides based on polyetheramines with other

monomers having vinylic or an allylic moiety to form polymers that exhibit surface

activity on par with traditional surfactants.

The anionic polymers of the present invention are soluble in water and exhibit

surface active properties like nonionic surfactants such as low critical micelle

concentration (CMC) and low surface tension in aqueous solution. The anionic surface

active water soluble polymers are prepared by copolymerizing polymerizable amides based on polyetheramines with other monomers having vinylic or an allylic moiety to form

polymers that exhibit surface activity on par with traditional surfactants. The polymerizable amides are made by reacting one or more polyetheramines (a.k.a.

polyoxyalkyleneamines) with maleic anhydride. These polymerizable amides can be hydrophilic or hydrophobic in nature. For example, in one embodiment of the present

invention, a hydrophobic SURFONAMINE® ML-300 amine is reacted with maleic

anhydride to form an amide which is then copolymerized with one or more hydrophilic monomers such as methacrylic acid, acrylic acid, or acrylamide to form a surface active polymer according to the following reaction scheme:

H₃C (CH₂)_H-13 O - CH₂

Surfonamine ML-300 Maleic Anhydride

CH₃ CH₃ O ^H H₃C (CH₂)_11-13 o CH₂CH ^■ CH₂CH NH C C = CH

COOH

Polymerizable amide

in which PO represents propylene oxide, and in which n is sufficient to yield a weight- average molecular weight in the range of between about 3000 and 100,000. In the second reaction step above, it is preferred to add the NaOH in a neutralization step after completion

of the reaction, and after the addition of the initiator.

Thus, the surface active copolymers of the invention are prepared by conventional polymerization techniques. Factors that affect the molecular weight of the product include

the amount of the initiator, the amount of the solvent (e.g., isopropyl alcohol), the reaction

time, amount of chain transfer agent - if used, etc. It is preferable to use ammonium

persulfate or sodium persulfate as an initiator; however, organic peroxide and azo initiators can also be used.

A random co-polymer according to one alternate embodiment of the invention has the structure:

in which n is sufficient to give a molecular weight in the range of between about 3,000 and

100,000. The first monomer in this co-polymer is prepared from maleic acid anhydride and

SURFONAMINE® ML-300 amine, and the second monomer in this co-polymer is prepared

from polyethylene glycol having methyl end caps ("MPEG"), and acrylic acid.

A random co-polymer according to another alternate embodiment of the invention

has the structure:

in which n is sufficient to give a molecular weight in the range of between about 3,000 and 100,000. This is the neutralized form of the polymer.

The following examples are provided as being exemplary of the present invention, and shall not be construed as being delimitive thereof in any manner.

Example 1 -preparation ofpolymerizable amide from SURFONAMINE ® MLSOO surfactant and maleic anhydride (ML-300 amide)

In a one liter round bottom flask equipped with a heating mantle and mechanical

stirrer are heated 300 g (1 mole) of SURFONAMINE® ML-300 amine to about 60° C

until homogeneous. 48.3 grams of powdered maleic acid anhydride are slowly added until

an exotherm occurs (approx. 10-15 minutes). Subsequently, 50 more grams of maleic

acid anhydride are further added at such a rate as to maintain the temperature below about

9O⁰C. After the addition of the maleic anhydride, the temperature is maintained at 80-90°

C for 90 minutes.

Example 2 - preparation of ML-300 amide (example l)/methacrylic acid copolymer (40% ML-300 amide: 60% Methactylic acid by weight) A 3-necked 1 L flask is fitted with a mechanical stirrer, heating mantle,

thermometer, reflux condenser, addition inlet, and provision for maintaining a nitrogen atmosphere within the reaction vessel. The flask is charged with 142 grams of isopropanol

and 104 grams of water. Heating is commenced under stirring and slow nitrogen sweep

until a gentle reflux is achieved, at about 80° C. A first stream comprising 74 grams of a

10% aqueous sodium persulfate solution was slowly added to the contents of the refluxing contents of the flask simultaneously with a second stream comprising a liquid mixture of

38 grams of SURFONAMINE® ML-300 amide monomer (Example 1) and 57 grams of

methacrylic acid, over the course of about 2 hours. Subsequently, an additional 15 grams

of 10% sodium persulfate was added and the temperature maintained at reflux for 1 hour to ensure complete reaction. To prepare a water-soluble salt of a copolymer, namely the

ammonium salt, the flask was set up for distillation by affixing a head and condenser. The

flask is heated until the azeotrope of isopropanol and water begins to distill and then 143 grams of 28% ammonium hydroxide aqueous solution is slowly added to the flask during the distillation at a rate which is approximately equal to the rate at which the azeotrope is

being distilled. When the temperature reaches 98-101° C, the flask is allowed to cool to

50° C and 128 grams of water is added to adjust a total solids content to about 22 %.

Figure 1 shows the surface tension curve for the above copolymer in water. As can be

seen, the polymer behaves like a surfactant and exhibits surface tension values of 30 dyne/cm at 1000 pm and 29 dyne/cm at 5000 ppm. Example 3 -preparation of ML-SOO amide (example l)/methacrylic acid copolymer (50% ML-300 amide: 50% Methacrylic acid by weight)

By the same procedure described in Example 2, 51 grams ML-300 amide and 51 grams methacrylic acid are copolymerized in isopropanol (151 grams) and water (110

grams) with 78 grams of 10% sodium persulfate aqueous solution. The polymer is neutralized with 107 grams Methanol amine (TEA) and about 136 grams of water is added

at the end to obtain 44 % solids. The surface tension curve for this copolymer is shown in Figure 2. It produces lower surface tension values at low concentrations than the

copolymer in Example 1. This can be attributed to a higher content of hydrophobic monomer, 50% vs. 40% by weight, in the copolymer. Again, the copolymer is quite

surface active as reflected by low surface tension.

Example 4 - Preparation of ML-300 amide (example l)/acrylamide copolymer (50% ML-300 amide: 50% acrylamide by weight)

By the same procedure described in Example 2, 58 grams ML-300 amide and 58 grams methacrylic acid are copolymerized in isopropanol (173 grams) and water (127

grams) with 90 grams of 10% sodium persulfate aqueous solution. The polymer is

neutralized with 22 grams triethanol amine (TEA) and about 156 grams of water is added

at the end to obtain 31 % solids. Figure 3 shows the surface tension of this copolymer in

water. This copolymer shows a distinct critical micelle concentration (CMC) at a very low concentration, 23 ppm and exhibits a minimum surface tension of 30 dyne/cm. Example 5 - Preparation of ML-SOO amide (example 1)/Methoxy PEG of methacrylic acid copolymer (30/70 by weight)

30 grams of SURFONAMHSfE® ML-300 amide, 70 grams of methoxy PEG

methacrylic acid, and 100 grams of propylene glycol were combined in a flask and stirred

under nitrogen. The mixture was heated to 115° C and 8 grams of solution containing tert-

butyl perbenzoate and butanol at 1:1 ratio by weight was added slowly over 1 hour. The

reaction was digested at 115° C for 2 hours, then stripped at 100° C for 1 hour under

vacuum. The surface tension of this copolymer is shown in Fig. 4. The cmc is about 30 ppm and the minimum surface tension is about 30 dyne/cm.

Example 6- High solids captan suspension usins example 4 co-polymer A stock solution of the following materials was first prepared: copolymer from

example 4 (6 parts), ethylene glycol (10 parts), NANS A® HS90/S (2 parts), deionized

water (82 parts). A slurry was then prepared from captan technical (200 grams) and the

stock solution (200 grams) by combining the materials and mixing by hand with a spatula.

This was milled for 3 minutes using an Eiger Mini- 100 media mill with 1.0 mm glass

media at 2500 rpm. The mill was kept cool during this process with cooling water at 0° C.

The captan particle size after milling was found to be in the 1-6 micron range, measured

using a Horiba LA-920 particle size analyzer.

Example 7 - Captan Suspension with MORWET ® D-425 dispersant

A stock solution of the following materials was first prepared: MORWET® D-425

(6 parts), ethylene glycol (10 parts), NANS A® HS90/S surfactant (2 parts), deionized

water (82 parts). A slurry was then prepared from captan technical (200 grams) and the stock solution (200 grams) by combining the materials and mixing by hand with a spatula. This was milled for 3 minutes using an Eiger Mini- 100 media mill with 1.0 mm glass

media at 2500 rpm. The mill was kept cool during this process with cooling water at 0 C.

The captan particle size after milling was found to be in the 1-6 micron range, measured using a Horiba LA-920 particle size analyzer.

The data below show that the invention provides a suspension with reduced

viscosity compared to the commercial dispersant standard MORWET®D-425 dispersant.

Data was generated with a Brookfield D VII+ Viscometer using an LV-2 spindle at 22° C.

The chart in FIG. 1 shows that the formulation made using the new polymeric dispersant

has a substantially lower viscosity than the same formulation made with MOR WET® D-

425 dispersant.

Thus, in a general sense, the present invention provides polymers made by

copolymerizing a first monomer comprising at least one ethylenically-unsaturated monomer and a second monomer described by the formula:

in which X is selected from the group consisting of: oxygen and — NR₄ — , wherein R₁ is independently selected from the group consisting of: hydrogen, and any C₁ to C₂₀ alkyl group; R₂ and R₃ are each independently selected from the group consisting of: any C₁ to C₆

alkyl group; and R₄ is independently selected from the group consisting of: hydrogen, and any C₁ to C₆ alkyl group. The at least one ethylenically-unsaturated monomer is preferably

selected from the group consisting of: acrylic acid, acrylamide, alkyl acrylates, alkyl

alkacrylates, ethyl acrylate, methyl methacrylate, allyl alcohol, and acrylonitrile.

Thus, the polymers useful as surfactants according to the present invention are described as having a weight-average molecular weight of any value between about 3,000

and 100,000 and whose structure contains a plurality of units having the general formula:

in which in which X is selected from the group consisting of: oxygen and — NR₄ — , wherein

Ri is independently selected from the group consisting of: hydrogen, and any Ci to C₂₀ hydrocarbyl group; R₂ and R₃ are each independently selected from the group consisting of:

any Ci to C₆ alkyl group; R₄ is independently selected from the group consisting of:

hydrogen, and any Ci to C₆ alkyl group; R₅ and R₆ are each independently selected from the

gi-oup consisting of: H, -CN, -CONH₂ (amide), -COOR₇ (ester), -CO₂H, -COO ^", and

in which R₇ is selected from the group consisting of: hydrogen, methyl, and ethyl; and wherein n is sufficient to yield a weight average molecular weight of said polymer of any

value in the range of between about 3,000 and 100,000.

Agriculturally-Active Materials

As used in this specification and the appended claims, the words "agriculturally

active material" means any chemical substance that: 1) when applied to a given foliage that

is generally regarded as undesirable adversely affects the longevity and/or reproductive capability of such foliage; or 2) when applied to a vicinity where insects dwell adversely

affects the longevity and/or reproductive capability of such insects; 3) is regarded by those skilled in the art as possessing agriculturally-beneficial properties, including insecticidal, herbicidal, fungicidal, and growth-enhancing properties. Include within this definition,

without limitation, are those chemical materials such as: 2,4,5-T, Acephate, Acetamiprid,

Acrinathrin, Aldicarb, Amitraz, Amitrole, Arsenic and its compounds, Bendiocarb, Benfuresate, Bensulfuron methyl, Bentazone, BHC, 2,4-D Bitertanol, Butarnifos, Butylate,

Cadusafos, Captafol(Difolatan), Captan, Carbaryl, Chinomethionat, Chlorfenvinphos,

Chlorfluazuron, Chlorimuron ethyl, Chlormequat, Chlorobenzilate, Chlorpropham,

Chlorpyrifos, Chlorthalonil, Cinmethylin, Clofentezine, Copper terephthalate trihydrate,

Cyanide compounds, Cyfluthrin, Cyhalothlin, Cyhexatin, Cypermethrin, Cyproconazole, Cyromazine, Daminozide, DCDP, DDT(including DDD₅DDE), Deltamethrin, Demeton, Diazinon, Dicamba, Dichlofluanid, Dichlorvos, Diclomezine, Dicofol(Kelthane), Dieldrin(

including Aldrin), Diethofencarb, Difenoconazole, Difenzoquat, Diflubenzuron,

Dimethipin, Dimethoate, Dimethylvinphos, Edifenphos, Endrin, EPN, EPTC, Esprocarb, Ethiofencarb, Ethofenprox, Ethoprophos, Ethoxyquin, Etobenzanide, Etrimfos, Fenarimol, Fenbutatin oxide, Fenitrothion, Fenobucarb, Fenpyroximate, Fensulfothion, Fenthion,

Fenvalerate, Flucythrinate, Flufenoxuron, Fluoroimide, Flusilazole, Flusulfamide, Flutolanil, Fluvalinate, Fosetyl, Fosthiazate, Glufosinate, Glyphosate, Guthion,

Halfenprox, Heptachlor (including Heptaclilor epoxide), Hexaflumuron, Hexythiazox, Imazalil, Imazosulfuron, Imibenconazole, Iminoctadine, Inabenfide, Inorganic bromide,

Iprodione, Isophenphos, Isoprocarb, Lead & its compounds, Lenacil, Malathion, Maleic hydrazide, MCPA (including Phenothiol), Mepanipyrim, Mephenacet, Mepronil, Methamidophos, Methiocarb, Methoprene, Methoxychlor, Metolachlor, Metribuzin,

Mirex, Myclobutanil, Nitenpyram, Oxamyl, Paclobutrazol, Parathion, Parathioii-methyl,

Pencycuron, Pendimethalin, Permethrin, Phenthoate, Phosalone( Rubitox), Phoxim, Picloram, Pirimicarb, Pirimiplios-methyl, Pretilachlor, Prohexadione, Propamocarb,

Propiconazole, Prothiofos, Pyraclofos, Pyrazoxyfen, Pyrethrins, Pyridaben, Pyridate, Pyrifenox, Pyrimidifen, Pyriproxyfen, Quinalphos, Quinclorac, Sethoxydim, Silafluofen,

Tebuconazole, Tebufenozide, Tebufenpyrad, Tecloftalam, Tefluthrin, Terbufos, Thenylchlor, Thiobencarb, Thiometon, Tralomethrin, Triadimenol, Tribenuron methyl,

Trichlamide, Trichlorfon, Triclofos-methyl, Tricyclazole, Triflumizole, and Vamidothion.

Agricultural Adjuvants

Adjuvants are chemical materials which are often employed as a component of an formulation containing one or more agriculturally active materials and which are designed to perform specific functions, including wetting, spreading, sticking, reducing evaporation, reducing volatilization, buffering, emulsifying, dispersing, reducing spray drift, and reducing foaming. No single adjuvant can perform all these functions, but different compatible adjuvants often can be combined to perform multiple functions

simultaneously; thus, adjuvants are a diverse group of chemical materials. Within the

meaning of the term "Adjuvants" is included any substance added to the spray tank to modify a pesticide's performance, the physical properties of the spray mixture, or both.

Spray application is perhaps the weakest link in the chain of events a pesticide follows through its development process. Some researchers claim that up to 70 percent of

the effectiveness of a pesticide depends on the effectiveness of the spray application. Selection of a proper adjuvant may reduce or even eliminate spray application problems associated with pesticide stability, solubility, incompatibility, suspension, foaming, drift,

evaporation, volatilization, degradation, adherence, penetration, surface tension, and

coverage, thereby improving overall pesticide efficiency and efficacy.

Surfactant adjuvants physically alter the surface tension of a spray droplet. For a

pesticide to perform its function properly, a spray droplet must be able to wet the foliage and spread out evenly over a leaf. Surfactants enlarge the area of pesticide coverage,

thereby increasing the pest's exposure to the chemical. Without proper wetting and

spreading, spray droplets often run off or fail to adequately cover these surfaces. Such

materials enhance the absorbing, emulsifying, dispersing, spreading, sticking, wetting or penetrating properties of pesticides. Surfactants are most often used with herbicides to

help a pesticide spread over and penetrate the waxy outer layer of a leaf or to penetrate through the small hairs present on a leaf surface. While surfactant adjuvants maybe anionic, cationic, or non-ionic, the non-ionic

surfactants are in most common usage. The "multi-purpose" non-ionic surfactants are

composed of alcohols and fatty acids, have no electrical charge and are compatible with most pesticides. Certain other surfactants maybe cationic (+ charge) or anionic (- charge) and are specialty adjuvants that are used in certain situations and with certain products.

Anionic surfactants are mostly used with acids or salts, and are more specialized and used

as dispersants and compatibility agents. Cationic surfactants are used less frequently but one group, the ethoxylated fatty amines, sometimes are used with the herbicide glyphosate.

Silicone-based surfactants are increasing in popularity due to their superior

spreading ability. Some of these surfactants are a blend of non-ionic surfactants (NIS) and

silicone while others are entirely a silicone. The combination of a NIS and a silicone

surfactant can increase absorption into a plant so that the time between application and rainfall can be shortened. There are generally two types of organo-silicone surfactants: the polyether-silicones that are soluble in water and the alkyl-silicones that are soluble in oil.

Unlike polyether-silicone types, alkyl-silicone surfactants work well with oil-based sprays,

such as dormant and summer oil sprays used in insect control. Alkyl-silicone-enhanced oil

sprays can maximize insecticidal activity and even allow significantly lower pesticide use rates that reduce residue levels on crops.

Sticker adjuvants increase the adhesion of solid particles to target surfaces. These

adjuvants can decrease the amount of pesticide that washes off during irrigation or rain.

Stickers also can reduce evaporation of the pesticide and some slow ultraviolet (UV) degradation of pesticides. Many adjuvants are formulated as spreader-stickers to make a general purpose product that includes a wetting agent and an adhesive. Extender adjuvants function like sticker surfactants by retaining pesticides longer

on the target area, slowing volatilization, and inhibiting UV degradation.

Plant penetrant surfactants have a molecular configuration that enhances

penetration of some pesticides into plants. A surfactant of this type may increase penetration of a pesticide on one species of plant but not another. Systemic herbicides,

auxin-type herbicides, and some translocatable fungicides can have their activity increased

as a result of enhanced penetration.

Compatibility agent adjuvants are especially useful when pesticides are combined

with liquid fertilizers or other pesticides, particularly when the combinations are physically or chemically incompatible, such as in cases when clumps and/or uneven distribution

occurs in the spray tank. A compatibility agent may eliminate problems associated with

such situations.

Buffers or pH modifier adjuvants are generally employed to prevent problems associated with alkaline hydrolysis of pesticides that are encountered when the pH of a

pesticide exceeds about 7.0 by stabilizing the pH at a relatively constant level. Extreme pH levels in the spray mixture can cause some pesticides to break down prematurely. This is particularly true for the organophosphate insecticides but some herbicides can break down

into inactive compounds in a matter of hours or minutes in alkaline situations (pH>7). For

example, the insecticide Cygon (dimethoate) loses 50 percent of its pest control power in

just 48 minutes when mixed in water of pH 9. At a pH of 6, however, it takes 12 hours for

degradation to progress to that extent. On the other hand, sulfonyl urea (SU) herbicides tend to break down more rapidly where the pH is below 7. At low pHs, the herbicide 2,4-D

is an uncharged molecule. At higher pH, 2,4-D tends to become more anionic or negatively charged which can affect its movement in the environment. Leaf coatings often

have a high pH that can contribute to poor performance with certain herbicides. The use of a buffering or acidifying adjuvant can stabilize or lower the pH of a spray solution

thereby improving the stability of the pesticide being used.

Mineral control adjuvants are used to mask the problems associated with water hardness minerals in spray water which can dimmish the effectiveness of many pesticides.

Mineral ions such as calcium, magnesium, salts and carbonates are commonly found in

hard water. These ions can bind with the active ingredients of some pesticides, especially the salt- formulation herbicides such as Roundup™ (glyphosate), Poast™ (sethoxydim),

Pursuit ™ (imazethapyr), and Liberty™ (glufosinate) resulting in poor weed control. The use of water-conditioning adjuvants gives hard water minerals something to bind with

other than the herbicide, hi addition, some ammonium sulfate-based adjuvants can be

used to offset hard water problems.

Drift retardant adjuvants improve on-target placement of pesticide spray by

increasing the average droplet size, since drift is a function of droplet size with drops with diameters of 100 microns or less tending to drift away from targeted areas.

Defoaming agent adjuvants are used to control the foam or frothy head often

present in some spray tallies that results from the surfactant used and the type of spray tank agitation system can often can be reduced or eliminated by adding a small amount of foam

inhibitor.

Thickener adjuvants increase the viscosity of spray mixtures which afford control over drift or slow evaporation after the spray has been deposited on the target area. Oil-based adjuvants have been gaining in popularity especially for the control of grassy weeds. There are three types of oil-based adjuvants: crop oils, crop oil concentrates (COC) and the vegetable oils. Crop Oil adjuvants are derivative of paraffin-based

petroleum oil. Crop oils are generally 95-98% oil with 1 to 2% surfactant/emulsifier. Crop oils promote the penetration of a pesticide spray either through a waxy plant cuticle or

through the tough chitinous shell of insects. Crop oils may also be important in helping solubilize less water-soluble herbicides such as Poast™ (sethoxydim), Fusilade™

(fluaziprop-butyl) and atrazine. Traditional crop oils are more commonly used in insect and disease control than with herbicides. Crop oil concentrates (COC) are a blend of crop oils (80-85%) and the non-ionic surfactants (15-20%). The purpose of the non-ionic

surfactant in this mixture is to emulsify the oil in the spray solution and lower the surface

tension of the overall spray solution. Vegetable oils work best when their lipophilic

characteristics are enhanced, and one common method of achieving this is by esterification of common seed oils such as rapeseed, soybean, and cotton. The methylated seed oils

(MSO) are comparable in performance to the crop oil concentrates, in that they increase penetration of the pesticide. In addition, silicone-based MSOs are also available that take

advantage of the spreading ability of the silicones and the penetrating characteristics of the MSOs.

The special purpose or utility adjuvants are used to offset or correct certain

conditions associated with mixing and application such as impurities in the spray solution, extreme pH levels, drift, and compatibility problems between pesticides and liquid

fertilizers. These adjuvants include acidifiers, buffering agents, water conditioners, anti- foaming agents, compatibility agents, and drift control agents. Fertilizer-based adjuvants, particularly nitrogen-based liquid fertilizers, have been frequently added to spray solutions to increase herbicide activity. Research has shown that the addition of ammonium sulfate to spray mixtures enhances herbicidal activity on a

number of hard-to-kill broadleaf weeds. Fertilizers containing ammonium nitrogen have increased the effectiveness of the certain polar, weak acid herbicides such as Accent™ (nicosulfuron), Banvel™ (dicamba), Blazer™ (acifluorfen-sodium), Roundup™

(glyphosate), Basagran™ (bentazon), Poast™ (sethoxydim), Pursuit™ (imazethapyr), and

2,4-D amine. Early fertilizer-based adjuvants consisted of dry (spray-grade) ammonium sulfate (AMS) at 17 lbs per 100 gallons of spray volume (2%). Studies of these adjuvants

has shown that Roundup™ uptake was most pronounced when spray water contained

relatively large quantities of certain hard water ions, such as calcium, sodium, and magnesium. It is thought that the ions in the fertilizer tied up the hard water ions thereby

enhancing herbicidal action.

As used in this specification and the appended claims, the word "hydrocarbyl",

when referring to a substituent or group is used in its ordinary sense, which is well-known

to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon

character. Examples of hydrocarbyl substituents or groups include: (1) hydrocarbon

(including e.g., alkyl, alkenyl, alkynyl) substituents, alicyclic (including e.g., cycloalkyl,

cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic

substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); (3) hetero substituents, that is, substituents

which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon

atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the

hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.)

Consideration must be given to the fact that although this invention has been

described and disclosed in relation to certain preferred embodiments, obvious equivalent

modifications and alterations thereof will become apparent to one of ordinary skill in this art upon reading and understanding this specification and the claims appended hereto. The

present disclosure includes the subject matter defined by any combination of any one of

the various claims appended hereto with any one or more of the remaining claims, including the incorporation of the features and/or limitations of any dependent claim, singly or in combination with features and/or limitations of any one or more of the other

dependent claims, with features and/or limitations of any one or more of the independent claims, with the remaining dependent claims in their original text being read and applied to

any independent claim so modified. This also includes combination of the features and/or limitations of one or more of the independent claims with the features and/or limitations of

another independent claim to arrive at a modified independent claim, with the remaining dependent claims in their original text being read and applied to any independent claim so

modified. Accordingly, the presently disclosed invention is intended to cover all such modifications and alterations.

Claims

What is claimed is:

1) A composition of matter useful in agricultural end-use formulations which comprises:

a) a polymer having a weight-average molecular weight of any value in the range of between about 3,000 to about 100,000, which polymer includes in its structure a plurality of units described by the formula:

in which X is selected from the group consisting of: oxygen and — NR₄ — , the sum of p and q is any value between about 0 and about 100, including 0 and 100, wherein R₁ is

independently selected from the group consisting of: hydrogen, and any Ci to C₂₀

hydrocarbyl group; R₂ and R₃ may each be the same or different, and when the same they are

selected from the group consisting of: any Ci to C₆ alkyl group, and when R₂ and R₃ are

different they are each independently selected from the group consisting of: any Ci to C₆ alkyl group; R₄ is independently selected from the group consisting of: hydrogen, and any Ci

to C₆ alkyl group; R₅ and R₆ are each independently selected from the group consisting of: H,

-CN, -CONH₂ (amide), -COOR₇ (ester), -CO₂H, -COO ; and

in which R₇ is selected from the group consisting of: hydrogen, methyl, and ethyl; and

wherein n is sufficient to yield a weight average molecular weight of said polymer of any value in the range of between about 3,000 and 100,000, including salts thereof; and

b) at least one agriculturally active material.

2) A composition according to claim 1 wherein said composition comprises particles of said agriculturally active material having said polymer disposed on the exterior surface of said particles.

3) A composition according to claim 2 wherein said particles have an average size diameter

I which is smaller than about 3 mm.

4) A composition according to claim 1 and further comprising: c) at least one agricultural adjuvant.

5) A composition according to claim 2 which contains less than about 1% water by weight

based on the total weight of said composition. 6) An aqueous solution comprising a composition according to claim 1, wherein water is

present in any amount between about 0.3% and about 98 % by weight based on the total weight of said solution.

7) An aqueous solution according to claim 6 wherein said agriculturally active material is present in any amount between about 2 and about 70 % by weight based on the total weight

of the solution.

8) An aqueous solution according to claim 6 wherein said polymer is present in any amount

between about 0.1 and about 10 % by weight based on the total weight of the solution.

9) An aqueous solution according to claim 6 and further comprising: c) at least one

agricultural adjuvant.