EP0627880A1 - Leaching inhibition of crop treating chemicals with polymers - Google Patents

Leaching inhibition of crop treating chemicals with polymers

Info

Publication number
EP0627880A1
EP0627880A1 EP93905976A EP93905976A EP0627880A1 EP 0627880 A1 EP0627880 A1 EP 0627880A1 EP 93905976 A EP93905976 A EP 93905976A EP 93905976 A EP93905976 A EP 93905976A EP 0627880 A1 EP0627880 A1 EP 0627880A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
copolymer
comonomer
polymer
alkenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP93905976A
Other languages
German (de)
French (fr)
Other versions
EP0627880A4 (en
Inventor
Kolazi S. Narayanan
Ratan K. Chaudhuri
Robert B. Login
Sohan L. Paul
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/843,325 external-priority patent/US5231070A/en
Priority claimed from US07/843,024 external-priority patent/US5229354A/en
Priority claimed from US07/843,025 external-priority patent/US5229355A/en
Priority claimed from US07/919,317 external-priority patent/US5283228A/en
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Priority to EP97116923A priority Critical patent/EP0823212A1/en
Priority to EP97116922A priority patent/EP0823211A1/en
Publication of EP0627880A1 publication Critical patent/EP0627880A1/en
Publication of EP0627880A4 publication Critical patent/EP0627880A4/en
Ceased legal-status Critical Current

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

Definitions

  • Agrichemical contamination is a growing concern since more than 12 different pesticides have been found in the ground water. Studies have shown that pesticide residues in ground water are increasing and are
  • herbicides such as bromacil, atrazine, metribuzin, dicamba and metolachlor, nematicides such as aldicarb, fungicides such as triforine, pencanazole and bendiocarb and insecticides such as diazinone,
  • leach inhibiting, copolymer which is readily combined with an agrichemical or incorporated into an agrichemical formulation.
  • the leach inhibiting copolymers of this invention are copolymers, preferably water insoluble copolymers having less than 10% water solubility, such as copolymers of maleic acid, a C 1 to C 6 mono- or di- ester of said acid or a mixture
  • alkenyl ether or an alpha olefin which copolymer has a molecular weight (Mw) of between about 8,000 and about 3,000,000.
  • Mw molecular weight
  • the structure of said copolymer is defined by the formula wherein X is C 1 to C 25 alkyl, alkoxy, aryl, aryloxy;
  • R 1 and R 2 are each independently hydrogen or C 1 to
  • n has a value of from 25 to 5000.
  • maleate esters examples include mono- and di- methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl and dimethylpropyl esters of maleic acid or mixtures thereof.
  • the polymer may also contain mixtures of maleic acid and at least one of the ester derivatives as the monomeric portion of the polymer.
  • alkyl alpha-alkenyl ether comonomer examples include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl pentyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl t-butyl ether, vinyl hexyl ether, vinyl methylbutyl ethers, 2-ethenyl butyl ether, 2-ethenyl propyl ether, 2-ethenyl ethyl ether, 2-ethenyl hexyl ether, 2-ethenyl dodecyl ether, 2-ethenyl benzyl ether, vinyl ethylbutyl ethers and mixtures thereof.
  • Illustrative of the comonomeric alpha olefins are ethene, propene, 1-butene, 1-octene, 1-hexadecene,
  • the preferred polymers of this invention are the copolymers of maleic acid or the C 1 to C 4 half esters of maleic acid with a methyl, ethyl or butyl vinyl ether having a molecular weight of between about 10,000 and about 1,000,000.
  • the above polymer/agrichemical is contacted with the plant or surrounding soil area in a pre-emergent or post-emergent application and in an effective leach
  • those containing between about 10 and about 90 weight % of the alkyl alkenyl ether monomer are desirable and those containing between about 10 and about 90 weight % of the alkyl alkenyl ether monomer are desirable and those
  • containing containing not more than 80 weight % of the comonomer are recommended for most plant species.
  • the present polymer is applied as an aqueous solution containing from about 25 to about 65 wt. % copolymer; although alcoholic solutions in the same
  • surfactants such as lignin sulfonate, naphthalene/formaldehyde condensate sulfonate, alkoxylated phenols, and the like can also be added in amounts up to about 5 wt. % of the total composition to increase
  • emulsifiers can also be included in the formulation if desired.
  • suspension aids can also be included in the formulation if desired.
  • preservatives can also be included in the formulation if desired.
  • inhibiting formulation can also be applied as a powder for crop dusting; in which case the formulation is dried to a particulate solid before use.
  • a further advantage of the present polymers is that they are non-toxic and are environmentally safe; thus they do not add to soil contamination. Additionally the present polymers may increase the organic content of the soil, thus benefiting future crops.
  • the leach inhibiting is accomplished with a nitrogen-containing carbohydrate polymer having pendant secondary, tertiary or quaternized amino groups which is readily formulated or incorporated with a plant treating agent to hinder or prevent migration of the plant treating agent into the ground water, aqua-system or soil areas vicinal to the treating site.
  • polymers are preferably derivatives of naturally occurring plant and animal polycarbohydrates and proteins, such as a hydrolyzed animal protein, e.g.
  • keratin a linear polycarbohydrate such as a polysacharide, e.g. starch, cellulose, guar gum or partially hydrolyzed polycarbohydrates of the above.
  • suitable polymers include the alkoxylated derivatives of vinyl alcohol polymer or vinyl alcohol/vinyl acetate copolymer.
  • the present leach inhibiting polymers of this invention are derivatized by the following general equation.
  • R is hydrogen or methyl
  • R 1 , R 2 and R 3 are each selected from the group of
  • R 1 , R 2 and R 3 is other than hydrogen
  • X- is an anion; a has a value of from 0 to 20 and b has a value of from 2 to 18.
  • the carbohydrate polymers of this invention include steardimonium hydroxyethyl cellulose; laurdimonium hydroxyethyl cellulose; cocadimonium hydroxyethyl
  • cellulose with a trimethyl ammonium hydroxypropylated epoxide or quaternized alkyl polyvinyl alcohol/acetate copolymer guar gum polymerized 2-hydroxy-3-(trimethyl ammonium) propyl ether chloride and the like.
  • X is hydrogen, a C 1 to C 22 radical of the group alkyl, alkoxy, aryl, alkaryl, aryloxy and alkaryloxy;
  • R 2 is hydrogen or -(CO) y! OR';
  • R, R 1 , R 3 and R' are each selected from the group of hydrogen and lower alkyl
  • x, y, y' and z each have a value of 0 or 1;
  • a has a value of from 2 to 4; Z is -O- or -NH-
  • Y is an optionally quaternized group of or
  • R 4 and R 5 are hydrogen or lower alkyl except that at least one of R 4 and R 5 is lower alkyl and mixtures of comonomer B.
  • the present copolymers possess superior leach inhibiting properties which is in part due to the
  • suitable alpha olefin units (A) include organo methyl vinyl ether, organo acrylate or methacrylate; organo vinyl alcohol; organo maleic acid; organo butyl maleate; maleic acid ethyl ester; acrylic or methacrylic acid; methyl, methacrylate or acrylate; maleic acid wherein said organo group is preferably C 2 to C 18 alkyl; phenyl optionally substituted with lower alkyl, lower alkoxy or alkenyl; benzyl; phenyloxy optionally substituted with lower alkyl and the like.
  • the copolymers of this invention are those having a number average molecular weight greater than 20,000, preferably between about 50,000 and about 150,000.
  • the polymers also having a polydispersity* of from about 4 to about 8, most desirably about 6, are considered the best for providing uniform formulations of high efficiency.
  • the preferred copolymers of this invention are those shown in following Table A.
  • lactam-containing polymer which is readily formulated with or incorporated into a plant treating agent which polymer is selected from the group of a crosslinked or
  • the lactam moiety of the polymer is represented by the formula
  • R is C 3 to C 6 alkylene optionally substituted with C 1 to C 20 alkyl; R 1 and R 2 are each
  • n independently C 2 to C 20 alkyl or hydrogen and n has a value of from 0 or 2.
  • lactam units include monocyclic lactams such as N-vinyl- and N-ethenylpyrrolidones, caprolactam; azacyclooctanones, as well as mono-, di- or tri- methyl, ethyl, octyl, hexadecyl,
  • N-alkenyl lactam polymers of this invention are those having a number average molecular weight of between about 5,000 and about 500,000, preferably between about 6,000 and about 150,000.
  • the polymers also having a polydispersity* of from about 1 to about 8, most desirably about 2-6, are considered the best for providing uniform formulations of high efficiency.
  • the present leach inhibitors those containing between about 0 and about 90 weight % of the non-lactam comonomer are useful; however, those containing not more than 85 weight % of a comonomer are recommended for most plant species.
  • the lactam species substituted or unsubstituted N-vinyl pyrrolidonyl-containing polymers are preferred.
  • the present leach controlling agents include C 20 alkylated N-vinyl pyrrolidone
  • polymers crosslinked N-vinyl pyrrolidone homopolymers, N-alkenyl pyrrolidone polymers with an alpha-olefin, such as propene or 1-butene; polyvinylpyrrolidinone/acrylic or methacrylic acid copolymer;
  • N-alkenyl pyrrolidone/vinyl acetate copolymer N-alkenyl pyrrolidone/vinyl acetate copolymer
  • N-alkenyl pyrrolidone/vinyl butyrate copolymer N-alkenyl pyrrolidone/vinyl butyrate copolymer
  • N-alkenyl pyrrolidone/maleic acid or anhydride copolymer N-alkenyl pyrrolidone/dimethylaminoethyl acrylamide copolymer
  • N-alkenyl caprolactam/dimethylaminoethyl methacrylate copolymer quaternized N-alkenyl caprolactam/dimethylaminoethyl
  • N-vinyl pyrrolidone/eicosene copolymer N-vinyl pyrrolidone/eicosene copolymer
  • a water soluble wetting agent for pesticide and herbicide formulations also is provided herein comprising 0.01 to 90% by weight higher alkyl lactam, 0.01 to 24% anionic surfactant and water.
  • An especially preferred embodiment utilizes a homogeneous aqueous solution
  • the higher alkyl lactam remains soluble, no phase separation occurring.
  • the wetting agent is uniformly dispersed in the required formulation, providing enhanced effectiveness and wetting ability at low cost.
  • the inventive wetting agent is totally biodegradable, avoiding aromatic components, ethylene oxide residuals or phosphates.
  • the wetting agent of the present invention contains one or more higher alkyl substituted lactams, an anionic surfactant and water.
  • higher alkyl refers to C 6 alkyl or higher and the term “lactams” is inclusive of caprolactam, valerolactam and pyrrolidone.
  • lactams as shown in formula I may be used in the invention.
  • n 3, 4 or 5 and n ⁇ 6.
  • the higher alkyl pyrrolidones of formula II are used.
  • R', R'' and R''' are H, lower alkyl, alkoxy, cycloalkyl, or aralkyl.
  • N-octyl-pyrrolidone N-dodecylpyrrolidone or mixtures thereof.
  • alkali metal salts of C 8 -C 22 aliphatic surfactants such as sodium dodecyl sulfate, sulfonate, alkali metal salts of alkyl aromatic sulfonates, sulfates, ethoxylated versions of the above, alkylphenyl ethoxylated phosphate esters, etc.
  • the anionic surfactants may form pseudo salts or io pairs with the higher-alkyl pyrrolidones, and are believed to produce synergistic effects on wetting and surface spreading.
  • the ranges of the various components may be 0.01 to 90% cyclic lactam, 0.01 to 24% anionic surfactant and water. Preferably, 35 to 65% cyclic lactam, 8 to 16% surfactant and water are used. More -preferred is a combination of 39 to 55% higher alkyl pyrrolidone, 10 to 14% surfactant, preferably, sodium dodecyl sulfate, and water.
  • the concentrate can be added to a commercial formulation at the rate of 0.1% to 0.5%.
  • a particular advantage of the invention is that the cyclic lactams promote solubility of the active ingredients in the formulation increasing uniformity in application together with enhanced wetting. The use of such materials as wetting agents in aqueous compositions would not be expected due to the perceived propensity for phase separation. However, the inventive formulation, utilizing an anionic surfactant with the cyclic lactam, precludes this from occurring.

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

Abstract

L'invention concerne le blocage de la lixiviation de produits chimiques utilisés dans le traitement des récoltes, dans les nappes d'eau souterraines, l'aqua-système et le sol environnant du site de traitement par mise en contact de la plante ou de l'emplacement de la plante avec une quantité efficace bloquant la lixiviation et tolérée par les plantes (a) d'un copolymère d'un acide maléique ou un ester ou un mélange de celui-ci, et d'un comonomère d'un alkyle alpha alcényle éther; ou (b) d'une protéine ou d'un polymère dérivé d'un glucide contenant de l'hydroxy libre et des groupes amino secondaires, tertiaires ou quaternisés; ou (c) d'un copolymère possédant des groupes amino ou de pyrrolidone éventuellement quaternisés libres; ou (d) d'un polymère contenant du lactame sélectionné dans le groupe constitué par un homopolymère ou un copolymère de N-alcényl lactame éventuellement réticulé avec un comonomère C2 à C30 sélectionné dans le groupe constitué par un acide alcénoïque, un alcényl-anhydride, un ester, un éther, un amino ester ou amino amide et une alpha mono ou dioléfine; comprenant éventuellement un agent mouillant à base d'eau d'un lactame substitué par un alkyle supérieur, un tensioactif anionique et de l'eau afin d'améliorer les propriétés de mouillage des formulations herbicides et pesticides.The invention relates to blocking the leaching of chemicals used in the treatment of crops, in groundwater, the aqua-system and the surrounding soil of the treatment site by contacting the plant or the location of the plant with an effective leach blocking and plant tolerated amount (a) of a copolymer of a maleic acid or an ester or a mixture thereof, and a comonomer of an alpha alkyl alkenyl ether; or (b) a protein or polymer derived from a carbohydrate containing free hydroxy and secondary, tertiary or quaternized amino groups; or (c) of a copolymer having optionally free quaternized amino or pyrrolidone groups; or (d) a polymer containing lactam selected from the group consisting of a homopolymer or copolymer of N-alkenyl lactam optionally crosslinked with a C2 to C30 comonomer selected from the group consisting of an alkenoic acid, an alkenyl anhydride, an ester, an ether, an amino ester or amino amide and an alpha mono or diolefin; optionally comprising a water-based wetting agent of a lactam substituted by a higher alkyl, an anionic surfactant and water in order to improve the wetting properties of the herbicidal and pesticidal formulations.

Description

LEACHING INHIBITION OF CROP TREATING
CHEMICALS WITH POLYMERS
Agrichemical contamination is a growing concern since more than 12 different pesticides have been found in the ground water. Studies have shown that pesticide residues in ground water are increasing and are
particularly severe where agronomic and horticultural crops are grown in permeable sandy soils or in locations which receive heavy rainfall. Among the chemicals which are particularly troublesome are herbicides such as bromacil, atrazine, metribuzin, dicamba and metolachlor, nematicides such as aldicarb, fungicides such as triforine, pencanazole and bendiocarb and insecticides such as diazinone,
chloropyrophor, and ethion, which have been found in drinking water. Hence, there is an acute need to restrict the downward movement of pesticides, herbicides, fungicides and other organic pollutants in the soil without reducing their agricultural efficacy.
(a) There is provided a leach inhibiting, copolymer which is readily combined with an agrichemical or incorporated into an agrichemical formulation. The leach inhibiting copolymers of this invention are copolymers, preferably water insoluble copolymers having less than 10% water solubility, such as copolymers of maleic acid, a C1 to C6 mono- or di- ester of said acid or a mixture
thereof and a C2 to C25 comonomer of an alkyl alpha
alkenyl ether or an alpha olefin, which copolymer has a molecular weight (Mw) of between about 8,000 and about 3,000,000. The structure of said copolymer is defined by the formula wherein X is C1 to C25 alkyl, alkoxy, aryl, aryloxy;
R1 and R2 are each independently hydrogen or C1 to
C6 alkyl and n has a value of from 25 to 5000.
Examples of suitable maleate esters include mono- and di- methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl and dimethylpropyl esters of maleic acid or mixtures thereof. The polymer may also contain mixtures of maleic acid and at least one of the ester derivatives as the monomeric portion of the polymer.
Representative examples of the alkyl alpha-alkenyl ether comonomer include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl pentyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl t-butyl ether, vinyl hexyl ether, vinyl methylbutyl ethers, 2-ethenyl butyl ether, 2-ethenyl propyl ether, 2-ethenyl ethyl ether, 2-ethenyl hexyl ether, 2-ethenyl dodecyl ether, 2-ethenyl benzyl ether, vinyl ethylbutyl ethers and mixtures thereof.
Illustrative of the comonomeric alpha olefins are ethene, propene, 1-butene, 1-octene, 1-hexadecene,
1-eicosene, 1-pentacosene, etc. and mixtures of any of the above comonomers.
The preferred polymers of this invention are the copolymers of maleic acid or the C1 to C4 half esters of maleic acid with a methyl, ethyl or butyl vinyl ether having a molecular weight of between about 10,000 and about 1,000,000. The above polymer/agrichemical is contacted with the plant or surrounding soil area in a pre-emergent or post-emergent application and in an effective leach
inhibiting, plant tolerating amount. In combining with the active agrichemical, as little as 0.001 weight % of instant polymer, based on the total composition, is effective to inhibit leaching with various agrichemicals. However a weight ratio of agrichemical to polymer of between about 0.1:1 and about 10:1 is recommended and between about 0.3:1 and about 2:1 is preferred.
Of the present polymeric leach inhibitors, those containing between about 10 and about 90 weight % of the alkyl alkenyl ether monomer are desirable and those
containing containing not more than 80 weight % of the comonomer are recommended for most plant species.
Generally the present polymer is applied as an aqueous solution containing from about 25 to about 65 wt. % copolymer; although alcoholic solutions in the same
concentration may also be employed.
Various surfactants, such as lignin sulfonate, naphthalene/formaldehyde condensate sulfonate, alkoxylated phenols, and the like can also be added in amounts up to about 5 wt. % of the total composition to increase
agrichemical solubility. Other adjuvants such as
emulsifiers, suspension aids and preservatives, can also be included in the formulation if desired. The leach
inhibiting formulation can also be applied as a powder for crop dusting; in which case the formulation is dried to a particulate solid before use.
A further advantage of the present polymers is that they are non-toxic and are environmentally safe; thus they do not add to soil contamination. Additionally the present polymers may increase the organic content of the soil, thus benefiting future crops. These and many other benefits will be realized by the use of the present
polymeric compounds. Various tests were conducted to show the efficacy and safety of the polymers in (a).
(b) As another feature of the invention, the leach inhibiting is accomplished with a nitrogen-containing carbohydrate polymer having pendant secondary, tertiary or quaternized amino groups which is readily formulated or incorporated with a plant treating agent to hinder or prevent migration of the plant treating agent into the ground water, aqua-system or soil areas vicinal to the treating site.
These polymers are preferably derivatives of naturally occurring plant and animal polycarbohydrates and proteins, such as a hydrolyzed animal protein, e.g.
keratin, a linear polycarbohydrate such as a polysacharide, e.g. starch, cellulose, guar gum or partially hydrolyzed polycarbohydrates of the above. Other suitable polymers include the alkoxylated derivatives of vinyl alcohol polymer or vinyl alcohol/vinyl acetate copolymer. The present leach inhibiting polymers of this invention are derivatized by the following general equation.
R is hydrogen or methyl
R1 , R2 and R3 are each selected from the group of
hydrogen and C1 to C20 alkyl, with the proviso that, in the above formula, at least one of R-^ and R2 or at
least one of R1, R2 and R3 is other than hydrogen;
X- is an anion; a has a value of from 0 to 20 and b has a value of from 2 to 18.
The carbohydrate polymers of this invention include steardimonium hydroxyethyl cellulose; laurdimonium hydroxyethyl cellulose; cocadimonium hydroxyethyl
cellulose; guar hydroxypropyl triammonium chloride; a polymeric quaternary ammonium salt of hydroxyethyl
cellulose with a trimethyl ammonium hydroxypropylated epoxide or quaternized alkyl polyvinyl alcohol/acetate copolymer; guar gum polymerized 2-hydroxy-3-(trimethyl ammonium) propyl ether chloride and the like.
Polymers having a number average molecular weight of between about 50,000 and about 1,000,000, preferably between about 60,000 and about 150,000, are suitable.
Those polymers having a polydispersity of from about 2 to about 8, most desirably between about 3 and 4, are
considered the best for providing uniform formulations of high efficiency.
Various tests were carried out to show the effectiveness of the polymers in (b). (c) In accordance with another feature of this invention, there is provided a leach inhibiting copolymer having pendant nitrogeneous groups which is readily formulated with or incorporated into a plant treating agent; which copolymer having pendant nitrogeneous groups contains between about 40 and about 98 wt. % of monomer unit A defined by the formula
.
and mixtures of comonomer A and 2 to 40 wt. % of comonomer unit B .
wherein X is hydrogen, a C 1 to C22 radical of the group alkyl, alkoxy, aryl, alkaryl, aryloxy and alkaryloxy;
R2 is hydrogen or -(CO)y!OR';
R, R1, R3 and R' are each selected from the group of hydrogen and lower alkyl;
R6 is hydrogen or 0=C I-[Z(CH20a ]z Y
x, y, y' and z each have a value of 0 or 1;
a has a value of from 2 to 4; Z is -O- or -NH-
Y is an optionally quaternized group of or and
R4 and R5 are hydrogen or lower alkyl except that at least one of R4 and R5 is lower alkyl and mixtures of comonomer B.
The present copolymers possess superior leach inhibiting properties which is in part due to the
quaternized, tertiary or secondary amino groups depending from the linear polymer chain. These pendant groups provide positively charged sites which can act as an anchoring groups for the negatively charged silicate soil surface.
Examples of suitable alpha olefin units (A) include organo methyl vinyl ether, organo acrylate or methacrylate; organo vinyl alcohol; organo maleic acid; organo butyl maleate; maleic acid ethyl ester; acrylic or methacrylic acid; methyl, methacrylate or acrylate; maleic acid wherein said organo group is preferably C2 to C18 alkyl; phenyl optionally substituted with lower alkyl, lower alkoxy or alkenyl; benzyl; phenyloxy optionally substituted with lower alkyl and the like. Illustrative of comonomer B units are The copolymers of this invention are those having a number average molecular weight greater than 20,000, preferably between about 50,000 and about 150,000. The polymers also having a polydispersity* of from about 4 to about 8, most desirably about 6, are considered the best for providing uniform formulations of high efficiency.
The preferred copolymers of this invention are those shown in following Table A.
(d) In still another embodiment of this
invention, there is provided a leach inhibiting,
lactam-containing polymer which is readily formulated with or incorporated into a plant treating agent which polymer is selected from the group of a crosslinked or
non-crosslinked N-alkenyl lactam homopolymer or copolymer with a C2 to C30 comonomer selected from the group of an alkenoic acid; an alkenyl- anhydride, ester, ether, amino ester, amino amide; and an alpha mono- or di- olefin and terpolymeric mixtures of the above monomers.
The lactam moiety of the polymer is represented by the formula
wherein R is C3 to C6 alkylene optionally substituted with C1 to C20 alkyl; R1 and R2 are each
independently C2 to C20 alkyl or hydrogen and n has a value of from 0 or 2.
Examples of suitable lactam units include monocyclic lactams such as N-vinyl- and N-ethenylpyrrolidones, caprolactam; azacyclooctanones, as well as mono-, di- or tri- methyl, ethyl, octyl, hexadecyl,
eicosyl, etc. ring substituted derivatives thereof. The N-alkenyl lactam polymers of this invention are those having a number average molecular weight of between about 5,000 and about 500,000, preferably between about 6,000 and about 150,000. The polymers also having a polydispersity* of from about 1 to about 8, most desirably about 2-6, are considered the best for providing uniform formulations of high efficiency.
* Wt. Av. Molecular weight (Mw)/No. Av. Molecular Weight (Mn) Of the present leach inhibitors, those containing between about 0 and about 90 weight % of the non-lactam comonomer are useful; however, those containing not more than 85 weight % of a comonomer are recommended for most plant species. Of the lactam species, substituted or unsubstituted N-vinyl pyrrolidonyl-containing polymers are preferred. Examples of the present leach controlling agents include C20 alkylated N-vinyl pyrrolidone
polymers; crosslinked N-vinyl pyrrolidone homopolymers, N-alkenyl pyrrolidone polymers with an alpha-olefin, such as propene or 1-butene; polyvinylpyrrolidinone/acrylic or methacrylic acid copolymer;
N-alkenyl pyrrolidone/propenoiσ acid copolymer;
N-alkenyl pyrrolidone/vinyl acetate copolymer;
N-alkenyl pyrrolidone/acrylic or methacrylic acid
copolymer;
N-alkenyl pyrrolidone/methyl vinyl ether copolymer;
N-alkenyl pyrrolidone/butadiene copolymer;
N-alkenyl pyrrolidone/vinyl butyrate copolymer;
N-alkenyl pyrrolidone/maleic acid or anhydride copolymer; N-alkenyl pyrrolidone/dimethylaminoethyl acrylamide copolymer;
quaternized N-alkenyl pyrrolidone/dimethylaminoethyl acrylamide copolymer;
N-alkenyl pyrrolidone/dimethylaminoethyl methacrylate copolymer;
quaternized N-alkenyl pyrrolidone/dimethylaminoethyl methacrylate copolymer;
N-vinyl pyrrolidone/N-vinyl caprolactam/dimethylaminoethyl methacrylate terpolymer;
N-alkenyl caprolactam/dimethylaminoethyl methacrylate copolymer; quaternized N-alkenyl caprolactam/dimethylaminoethyl
acrylate copolymer;
N-vinyl pyrrolidone/eicosene copolymer;
1-ethenyl-2-pyrrolidinone/acetic acid ethenyl ester
copolymer;
N-alkenyl pyrrolidone/acrylic acid copolymer;
water-insoluble crosslinked polyvmylpyrrolidone or
polyethenylpyrrolidone copolymers, and the like.
Particularly preferred are the vinyl pyrrolidone polymers shown in following Table B.
TABLE B
Mn Mw
Binear poly(eicosenyl 7,000-10,000 40,000-60,0 N-vinyl eicosyl-pyrrolidone
graft polymer
N-vinylpyrrolidone/vinyl 8,000-12,000 40,000-60,0 acetate copolymer (60/40)
Polyvinylpyrrolidone/acrylic 30,000-60,000 100,000-300,0 acid copolymer (50/50)
Crosslinked polyvinyl- 80,000-120,000 800,000-1,200 pyrrolidone
N-vinylpyrrolidone/1- 15,000-17,000 40,000-60, butene graft polymer
Linear quaternized or > 1,000,000 *
non-quaternized N-vinylpyrrolidone/N-vinyl
caprolactam/dimethylaminoethyl methacrylate terpolymer
Linear quaternized or > 1,000,000 *
non-quaternized N-vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer
* Mn/Mw A water soluble wetting agent for pesticide and herbicide formulations also is provided herein comprising 0.01 to 90% by weight higher alkyl lactam, 0.01 to 24% anionic surfactant and water. An especially preferred embodiment utilizes a homogeneous aqueous solution
containing 55% N-octyl-2-pyrrolidone, 14% sodium dodecyl sulfate, and water which can be diluted further to any concentration at less than or equal to 15% of the
formulation.
In the prescribed combination, the higher alkyl lactam remains soluble, no phase separation occurring.
Thus, the wetting agent is uniformly dispersed in the required formulation, providing enhanced effectiveness and wetting ability at low cost. In addition, the inventive wetting agent is totally biodegradable, avoiding aromatic components, ethylene oxide residuals or phosphates.
The wetting agent of the present invention contains one or more higher alkyl substituted lactams, an anionic surfactant and water. For purposes of this disclosure the term "higher alkyl" refers to C6 alkyl or higher and the term "lactams" is inclusive of caprolactam, valerolactam and pyrrolidone. The lactams as shown in formula I may be used in the invention.
Where m = 3, 4 or 5 and n ≤ 6. Preferably, the higher alkyl pyrrolidones of formula II are used.
Where n = 6-20, R', R'' and R''' are H, lower alkyl, alkoxy, cycloalkyl, or aralkyl.
Most preferred are N-octyl-pyrrolidone, N-dodecylpyrrolidone or mixtures thereof.
As the anionic surfactant, alkali metal salts of C8-C22 aliphatic surfactants such as sodium dodecyl sulfate, sulfonate, alkali metal salts of alkyl aromatic sulfonates, sulfates, ethoxylated versions of the above, alkylphenyl ethoxylated phosphate esters, etc., may be used, the anionic surfactants may form pseudo salts or io pairs with the higher-alkyl pyrrolidones, and are believed to produce synergistic effects on wetting and surface spreading.
The ranges of the various components may be 0.01 to 90% cyclic lactam, 0.01 to 24% anionic surfactant and water. Preferably, 35 to 65% cyclic lactam, 8 to 16% surfactant and water are used. More -preferred is a combination of 39 to 55% higher alkyl pyrrolidone, 10 to 14% surfactant, preferably, sodium dodecyl sulfate, and water. When used as a concentrate, the concentrate can be added to a commercial formulation at the rate of 0.1% to 0.5%. A particular advantage of the invention is that the cyclic lactams promote solubility of the active ingredients in the formulation increasing uniformity in application together with enhanced wetting. The use of such materials as wetting agents in aqueous compositions would not be expected due to the perceived propensity for phase separation. However, the inventive formulation, utilizing an anionic surfactant with the cyclic lactam, precludes this from occurring.
Various tests were conducted to confirm the efficacy of utilizing the above referenced wetting agent in a pesticide or herbicide formulation.

Claims

WHAT IS CLAIMED IS:
1. A leach inhibiting agrichemical composition comprising an active agrichemical, an inactive carrier and a leach inhibiting amount of (a) a copolymer of maleic acid, the corresponding C1 to C6 alkyl ester or
mixtures thereof and a C2 to C25 comonomer of an alkyl alpha alkenyl ether or an alpha olefin; said copolymer having a Mw between about 8,000 and about 3,000,000; or (b) a polymer having pendant hydroxy and amino groups and defined by the formula
wherein the polymer moiety is selected from the group of a naturally occurring carbohydrate or hydroxylated protein polymer, a vinyl alcohol homopolymer and a vinyl
alcohol/vinyl acetate copolymer;
R is hydrogen or methyl;
Y is , ,
or
where R1, R2 and R3 are each selected from the group of hydrogen and C1 to C20 alkyl, with the proviso that at least one of R1 and R2 or at least one of R1, R2 and R3 is other than hydrogen;
X- is an anion;
a has a value of from 0 to 20 and
b has a value of from 2 to 18; or (c) a polymer having pendent nitrogeneous groups which polymer contains between about 40 and about 98 wt. % of monomer unit A defined by the formula .
and mixtures of said monomers and 2 to 40 wt. % of
comonomer unit B .
wherein X is hydrogen, a C1 to C22 radical of the group alkyl, alkoxy, aryl, alkaryl, aryloxy and alkaryloxy;
R2 is hydrogen or -(CO)y'OR';
R, R1, R3 and R' are each selected from the group of hydrogen and lower alkyl;
R6 is hydrogen or
x, y, y' and z each have a value of 0 or 1;
a has a value of from 2 to 4;
Z is -O- or -NH-
Y is an optionally quaternized group of or
and R4 and R5 are hydrogen or lower alkyl except that at least one of R4 and R5 is lower alkyl; said copolymer having a number average molecular weight greater than
20,000; or (d) a crosslinked or non-crosslinked N-alkenyl lactam homopolymer or a copolymer with a C2 to C30
comonomer selected from the group of an alkenoic acid;
alkenyl anhydride, alkenyl ester, alkenyl ether, optionally quaternized alkenyl amino amide, optionally quaternized alkenyl amino ester, an alpha mono- or di- olefinically unsaturated comonomer, and terpolymeric mixtures of said comonomers; optionally including a water based wetting agent for pesticide formulations comprising 0.01 to 90% higher alkyl lactam, 0.01 to 24% anionic surfactant and water.
2. The composition of claim 1 wherein, in (a), the copolymer contains between about 10 and about 90 wt. % of comonomer, the weight ratio of agrichemical to copolymer is between about 0.1:1 and about 10:1, and the copolymer is the copolymer of maleic acid and a comonomer which is a C1 to C4 alkyl vinyl ether.
3. The composition of claim 1 wherein, in (b), said polymer moiety is a polycarbohydrate, such as
quaternized alkyl polyvinyl alcohol/acetate copolymer, or a guar gum.
4. The composition of claim 1 wherein, in (c), the polymer is the polymer of maleic acid, a C1 to C4 alkyl vinyl ether and a comonomer wherein Z is -NH-, z is one, a is two and Y is a pyrrolidonyl radical, or a polymer of a C1 to C4 alkyl ester of maleic acid, a C1 to
C4 vinyl ether and a comonomer mixture of one comonomer wherein z is zero and Y is octadecylamine and another comonomer wherein Z is -NH-, z is one, a is two and Y is a pyrrolidonyl radical, or the polymer of maleic acid, a C1 to C4 alkyl vinyl ether and a comonomer wherein Z is
-NH-, z is one a is three, and Y is -N(CH3)2, or the polymer of maleic acid, a C1 to C4 alkyl vinyl ether and a comonomer mixture of one monomer where Z is -NH-, z is one, a is 3, and Y is -N(CH3)2 and another comonomer wherein z is zero and Y is octadecylamine.
5. The composition of claim 1 wherein said lactam moiety is represented by the formula
wherein R is C3 to Cg alkylene optionally substituted with C1 to C20 alkyl; R1 and R2 are each
independently hydrogen or C2 to C20 alkyl and n has a value of from 0 to 1 or a mixture of said lactam radicals.
6. The composition of claim 1 wherein, in the optional wetting agent, the higher alkyl substituted lactam is a pyrrolidone of the following formula:
where n = 6-20 (branched or linear), R', R'' and R''' are H, lower alkyl, alkoxy, cycloalkyl, or aralkyl, including N-octyl-2-pyrrolidone, N-isooctyl pyrrolidone,
N-dodecyl-2-pyrrolidone, N-octadecyl-2-pyrrolidone and mixtures thereof, and the anionic surfactant is an alkali metal salt of C8-C22 aliphatic surfactants, including sodium dodecyl sulfate, sulfonate, alkali metal salts of alkyl aromatic sulfonates, sulfates, and ethoxylated versions thereof, including sodium dodecyl sulfate, and, preferably, from 35-65% of the higher alkyl substituted lactam, and from 8-16% of the anionic surfactant is present.
EP93905976A 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers. Ceased EP0627880A4 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97116923A EP0823212A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers
EP97116922A EP0823211A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US920082 1978-06-28
US843025 1992-02-28
US843325 1992-02-28
US07/843,325 US5231070A (en) 1992-02-28 1992-02-28 Leaching inhibition of crop treating chemicals with lactam containing polymers
US843024 1992-02-28
US07/843,024 US5229354A (en) 1992-02-28 1992-02-28 Leaching inhibition of crop treating chemicals with nitrogen containing polymers
US07/843,025 US5229355A (en) 1992-02-28 1992-02-28 Leaching inhibition of crop treating chemicals with polymers
US92008292A 1992-07-27 1992-07-27
US07/919,317 US5283228A (en) 1992-07-27 1992-07-27 Leaching inhibition of crop treating chemicals with amino containing polymers
PCT/US1993/001362 WO1993016592A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers
US919317 1997-08-28

Related Child Applications (2)

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EP97116922A Division EP0823211A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers
EP97116923A Division EP0823212A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers

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EP0627880A1 true EP0627880A1 (en) 1994-12-14
EP0627880A4 EP0627880A4 (en) 1997-04-16

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EP97116922A Withdrawn EP0823211A1 (en) 1992-02-28 1993-02-16 Leaching inhibition of crop treating chemicals with polymers
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JP (1) JPH07504195A (en)
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FR2790642A1 (en) * 1999-03-08 2000-09-15 Aventis Cropscience Sa NEW PESTICIDE AND / OR REGULATORY GROWTH COMPOSITIONS

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FR2246572A1 (en) * 1973-10-02 1975-05-02 Hydrophilics Int Inc Hydrophilic copolymer salts of amino (meth) acrylate - and hydrophobic monomer, for delayed release of agricultural chemicals
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WO1989008127A1 (en) * 1988-02-29 1989-09-08 Gaf Chemicals Corporation Solubilization of complexes of water-insoluble organic compounds by aqueous solutions of polyvinylpyrrolidone

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DE2031989A1 (en) * 1969-07-09 1971-01-21 Ceskoslovenska Akademie Ved, Prag Pesticide preparations and processes for their manufacture
FR2246572A1 (en) * 1973-10-02 1975-05-02 Hydrophilics Int Inc Hydrophilic copolymer salts of amino (meth) acrylate - and hydrophobic monomer, for delayed release of agricultural chemicals
US4036788A (en) * 1975-02-11 1977-07-19 Plastomedical Sciences, Inc. Anionic hydrogels based on heterocyclic N-vinyl monomers
WO1989008127A1 (en) * 1988-02-29 1989-09-08 Gaf Chemicals Corporation Solubilization of complexes of water-insoluble organic compounds by aqueous solutions of polyvinylpyrrolidone

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CA2145212A1 (en) 1993-09-02
EP0627880A4 (en) 1997-04-16
AU663772B2 (en) 1995-10-19
EP0823212A1 (en) 1998-02-11
EP0823211A1 (en) 1998-02-11
AU3668593A (en) 1993-09-13
JPH07504195A (en) 1995-05-11

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