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.
• 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.
• herbicides such as bromacil, atrazine, metribuzin, dicamba and metolachlor
• nematicides such as aldicarb
• fungicides such as triforine
• insecticides such as diazinone, chloropyrophor, and
• 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- ⁇ to C 6 mono- or di- ester of said acid or a mixture thereof and a C 2 to C 25 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.
• Mw molecular weight
• X is C-L to C 2$ alkyl, alkoxy, aryl, aryloxy; R 1 and R 2 are each independently hydrogen or C- ⁇ to C 6 alkyl and 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, 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 C ⁇ 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-e ergent or post-emergent application and in an effective leach inhibiting, plant tolerating amount.
• 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.
• 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 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) .
• 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 l f R 2 and R 3 are each selected from the group of hydrogen and C. ⁇ to C 20 alkyl, with the proviso that, in the above formula, at least one of R- ⁇ and R 2 or at least one of lf 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; 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.
• X is hydrogen, a C- ⁇ to C 22 radical of the group alkyl, alkoxy, aryl, alkaryl, aryloxy and alkaryloxy;
• R 2 is hydrogen or -(CO) y! OR';
• R, R lf R 3 and R' are each selected from the group of hydrogen and lower alkyl
• Y is an optionally quaternized group of and
• 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 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.
• 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.
• Illustrative of comonomer B units are examples of comonomer B units.
• 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.
• Methylvinylether/maleic acid polymer having about 60 mole % of the maleic acid units converted to N-[3-(2-oxo-l-pyrrolidonyl) ethyl] amide units 50,000-100,000
• Methylvinylether/maleic acid having 40 mole % of the maleic acid units converted to
• Methyl vinyl ether/maleic acid polymer having about 60 mole % of the maleic acid units converted to
• Methyl vinyl ether/maleic acid polymer having about 10 mole % of the maleic acid units converted to N-octadecyl-amide units and 50 mole % of maleic acid converted to N-[3-(N,N-dimethylamino) propyl] amide units 50,000-100,000
• ** AMPHOMER ® is a polymer supplied by National Starch & Chemical Corp. , defined as a copolymer of octylacrylamide, t-butylaminoethyl methacrylate and 2 or more monomers of acrylic acid, methacrylic acid or their esters
• ULTRAH0LD ® 8 is a polymer supplied by BASF, defined as a terpolymer of acrylic acid, ethyl acrylate and N-t-butyl acrylamide
• 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 C 2 to C 30 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
• R is C 3 to Cg alkylene optionally substituted with C- j _ to C 20 alkyl; R and R 2 are each 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-ethenyl- pyrrolidones, 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.
• Examples of the present leach controlling agents include C 2Q 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/propenoi ⁇ acid copolymer N-alkenyl pyrrolidone/vinyl acetate copolymer; N-alkenyl pyrrolidone/acrylic or methacrylic acid copolymer;
• N-alkenyl pyrrolidone/ ethyl 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/di ethylaminoethyl acrylamide copolymer; quaternized N-alkenyl pyrrolidone/dimethylaminoethyl acrylamide copolymer;
• N-alkenyl pyrrolidone/dimethylaminoethyl methacrylate copolymer quaternized N-alkenyl pyrrolidone/dimethylaminoethyl methacrylate copolymer;
• N-alkenyl caprolactam/dimethylaminoethyl methacrylate copolymer quaternized N-alkenyl caprolactam/dimethylaminoethyl acrylate copolymer
• N-vinyl pyrrolidone/eicosene copolymer N-vinyl pyrrolidone/eicosene copolymer
• l-ethenyl-2-pyrrolidinone/acetic acid ethenyl ester copolymer N-vinyl pyrrolidone/eicosene copolymer
• l-ethenyl-2-pyrrolidinone/acetic acid ethenyl ester copolymer N-vinyl pyrrolidone/eicosene copolymer
• l-ethenyl-2-pyrrolidinone/acetic acid ethenyl ester copolymer N-vinyl pyrrolidone/eicosene copolymer
• l-ethenyl-2-pyrrolidinone/acetic acid ethenyl ester copolymer N-vinyl pyrrolidone/eicosene
• N-alkenyl pyrrolidone/acrylic acid copolymer water-insoluble crosslinked polyvmylpyrrolidone or polyethenylpyrrolidone copolymers, and the like.
• 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.
• 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 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
• R' • and R' • ' are H, lower alkyl, alkoxy, cycloalkyl, or aralkyl.
• N-octyl-pyrrolidone N-dodecylpyrrolidone or mixtures thereof.
• alkali metal salts of Cg-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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• 1993
  • 1993-02-16 CA CA 2145212 patent/CA2145212A1/en not_active Abandoned
  • 1993-02-16 EP EP97116922A patent/EP0823211A1/en not_active Withdrawn
  • 1993-02-16 WO PCT/US1993/001362 patent/WO1993016592A1/en not_active Application Discontinuation
  • 1993-02-16 AU AU36685/93A patent/AU663772B2/en not_active Ceased
  • 1993-02-16 EP EP93905976A patent/EP0627880A4/en not_active Ceased
  • 1993-02-16 JP JP5514918A patent/JPH07504195A/ja active Pending
  • 1993-02-16 EP EP97116923A patent/EP0823212A1/en not_active Withdrawn

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