EP0577627A1 - Couches d'arret biodegradables, a reticulation ionique et covalente, composees d'un polymere ionomere - Google Patents

Couches d'arret biodegradables, a reticulation ionique et covalente, composees d'un polymere ionomere

Info

Publication number
EP0577627A1
EP0577627A1 EP92906040A EP92906040A EP0577627A1 EP 0577627 A1 EP0577627 A1 EP 0577627A1 EP 92906040 A EP92906040 A EP 92906040A EP 92906040 A EP92906040 A EP 92906040A EP 0577627 A1 EP0577627 A1 EP 0577627A1
Authority
EP
European Patent Office
Prior art keywords
polymer
fertilizer
coated
fertilizers
coating
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.)
Withdrawn
Application number
EP92906040A
Other languages
German (de)
English (en)
Other versions
EP0577627A4 (en
Inventor
Pacifico V. Nanalastas
Evelyn N. Drake
Warren A. Thaler
Edward N. Kresge
Chester W. Elspass
Vijay Swarup
Albert J. Geiger
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0577627A1 publication Critical patent/EP0577627A1/fr
Publication of EP0577627A4 publication Critical patent/EP0577627A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • A01N25/26—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 in coated particulate form
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur

Definitions

  • This invention relates to an unsupported polymeric film as well as an encapsulated water soluble fertilizer or pesticide, or herbicide products which comprises a polymeric film of about 1 to about 100 micrometers coated on a surface of said fertilizer, said polymeric film comprising a covalently, crosslinked, sulfonated polymer having about 10 to about 200 meq of sulfonate groups per 100 grams of said covalently crosslinked sulfonated polymer, said sulfonate groups being neutralized with a polycaprolactone polymer being characterized by the formula
  • Ri or R2 is an alkyl, cycloalkyl or aryl group
  • R3, R and R5 are a hydrogen or alkyl, cycloalkyl, or aryl groups
  • m equals 1 to 20 and n equals 1 to 500.
  • the present invention relates to controlled release materials, e.g., fertilizers, micronutrients, herbicides, pesticides, and particularly to fertilizer-pesticide compositions.
  • the invention is more particularly directed to fertilizers and fertilizer-pesticide compositions to which thin film or ultrathin films or coatings of ionically and covalently crosslinked sulfonated polymers and a ine terminated polycaprolactone have been applied as an improved con ⁇ trolled release agent.
  • the present invention is directed to methods for producing fertilizer and fertilizer-pesticide composites coated with sulfonated polymers in addition to agricultural processes involving the use of such coated fertilizers and fertilizer- pesticide composites.
  • agricultural processes in which the fertilizer and fertilizer-pesticide composites coated with ionically and covalently crosslinked sulfonated polymers and amine terminated polycaprolactone in accordance with the present invention may be applied include processes for enhancing vegetation including plant growth stimulation and regulation as well as stimulation of seed germination.
  • the present invention relates to the compositions of associ ⁇ ating polymer protective barrier films, which will protect materials, such as agricultural chemicals, for a period of time and then degrade and release the encapsulated contents to the environment. More specifically, this invention relates to the preparation of ionomer compositions containing compatibilized polymers which will be degraded by microorganisms.
  • This invention provides new polymeric systems capable of degrading to a crumbly friable mass. These systems are based on the ability to produce compatible polymeric films from ionically and covalently crosslinked sulfonated polymers and amine terminated poly ⁇ caprolactone.
  • the ionically and covalently crosslinked sulfonated polymer can be in the free acid form or neutralized with a metal which can coordinate with the amine.
  • the combination makes excellent coatings, films and mechanical goods due to the compatibilization of the multiple polymer blend.
  • the degradability comes from the inherent characteristic of polycaprolactone, susceptibility to biodegradation.
  • the advent of plastics has introduced improved methods of packing goods.
  • polyethylene and polypropylene films, bags and bottles and polystyrene foam cups have the advantages of being chemically resistant, mechanically tough, light in weight and inexpensive.
  • plastics in packaging has led to the appearance of such materials in litter. While littered plastic articles are no more objectionable than littered articles of other materials, such as paper objects and metal cans, it has been suggested that the impact of plastic litter can be minimized by the development of plastic materials capable of undergoing chemical degradation upon exposure to the natural environment.
  • the present invention describes a polymer system which is biodegradable in film form.
  • the polymer system of the instant inven ⁇ tion comprises a compatible mixture of an ionically and covalently crosslinked sulfonated polymer with an amine terminated polycaprol ⁇ actone.
  • Compatible mixtures of sulfonated elastomeric polymers and amine terminated polycaprolactone are described in U.S. Patent No. 4,421,898; however, U.S. Patent No. 4,421,898 failed to teach or recognize the use of these polymer mixtures in their film form as an agricultural mulch.
  • Carbon, hydrogen, oxygen, nitrogen, phosphorus and sulphur are the primary elements essential to plant growth. Soils contain all of these elements in addition to other macro and micronutrients that enhance plant growth. Typically, however, such elements are seldom present in the soil in sufficient quantity or in forms that can support maximum plant productivity and yield. Therefore, fertilizers having specific chemical formulations and in pre-determined amounts must be added to enrich the soil to ensure maximum plant yield. The amount and form of the fertilizer added are pre-determined by chemi ⁇ cally assaying the amount and availability of the required nutrient(s) in the soil, for example, as disclosed by Methods of Soil Analysis, 1982, Amer. Soc. Agronomy, Madison, WI. Thus, appropriate fertilizer is added in amounts calculated to ensure the required plant yield based on known fertilizer response curves established by extensive agronomic testing for the particular plant and plant growth environ ⁇ ment.
  • Fertilizers containing nitrogen, phosphorus, sulphur and/or potassium may be applied as solid granules or in liquid form. These primary fertilizers may be supplemented with certain micronutrient trace elements such as copper, iron, manganese, zincj cobalt, molybdenum, boron usually supplied as oxides or salts containing the elements in the cationic form. Suitable salts are, for example, sulphates, nitrates, chlorides, molybdates or borates. The difference between trace element deficiency and toxicity, however, is but a few parts per million as measured by the concentration of the element in the soil.
  • the efficiency of utilization of fertilizers i.e., the percent uptake of the applied fertilizers is notoriously low.
  • chemical, biological and physical processes compete with the plant for the added fertilizer nutrients usually to the detriment of plant productivity.
  • nitrogen fertilizers added to the soil may be leached into groundwater, chemi ⁇ cally immobilized into clay minerals, chemically removed by volatiliz ⁇ ing of ammonia, biologically removed from the soil by denitrification to dinitrogen and nitrous oxide gases or immobilized into the active microbial biomass.
  • the lateral stress tending to rupture a film is inversely proportional to an exponential power of the film thickness. The thinner the film, the more easily it will rupture.
  • Polymers containing associating ionic groups, i.e. ionomers, which have a high degree of molecular interactions make excellent protective films. Covalently crosslinking networks of ionomers containing associating ionic groups can further improve the strength and barrier performance of these coatings.
  • the present invention relates to a process for preparing a polymeric film composition which is susceptible to chemical degrada ⁇ tion in the environment by preparing a composition comprising a compatible mixture of an ionically and covalently, crosslinked, sulfonated polymer and an amine terminated polycaprolactone, and subsequently subjecting the prepared composition in the form of a polymeric film to be a biodegrading environment.
  • the present invention also relates to coating vegetation enhancement agents, such as fertilizers and fertilizer- pesticide combinations, with thin or ultra-thin coatings of ionically and covalently crosslinked sulfonated polymers with an amine termin ⁇ ated polycaprolactone to result in controlled release fertilizers and fertilizer-pesticide combinations having improved barrier properties, as well as agricultural processes involving methods of using ferti ⁇ lizers and fertilizer-pesticide combinations coated with ionically and covalently crosslinked sulfonated polymers with amine terminated polycaprolactone in accordance with the present invention so as to decrease dissolution of soluble fertilizer components, increase fertilizer use efficiency and substantially decrease losses of the added fertilizer from the plant growth medium due to biological, chemical, or physical processes competing with the plant for the said nutrients.
  • vegetation enhancement agents such as fertilizers and fertilizer- pesticide combinations
  • the thin polymeric coatings are coated on vegetation enhance ⁇ ments, e.g., fertilizer or fertilizer/pesticide combinations.
  • the process of the instant invention generally comprises an organic solution of a water insoluble carboxylated polymer with a crosslinking agent which is not activated until a temperature of 40"C is obtained; coating the organic solution of the water insoluble sulfonated polymer and an amine terminated polycaprolactone and the crosslinking agent onto a substrate and subjecting the coated sub ⁇ strate to a temperature of at least 40°C to activate the crosslinking agent thereby covalently crosslinking the sulfonated polymer.
  • An alternative process comprises coating an organic solution of the water insoluble sulfonated polymer and amine terminated polycaprolactone onto the substrate and subsequently subjecting the coated substrate to an election beam thereby covalently crosslinking the water insoluble sulfonated polymer.
  • a still alternative process comprises coating a substrate with an organic solution of water insoluble sulfonated polymer and amine terminated polycaprolactone and subsequently con ⁇ tacting the coated substrate with a vapor or solution of sulfur monochloride thereby forming a covalently crosslinked water insoluble sulfonated polymer.
  • any one or all three of these processes in conjunction could be used to crosslink the water insoluble sulfonated polymer and amine terminated polycaprolactone. It is also contemplated that the water insoluble sulfonated polymer and amine terminated polycaprol ⁇ actone could be covalently crosslinked either in solution or in a solid form to form a formed, unsupported polymeric article having a thickness of 0.5 to about 40 mils by any one of the aforementioned processes.
  • the component materials of the instant process generally include a water insoluble sulfonated polymer and amine terminated polycaprolactone dissolved in an organic solvent system to form a solution with a concentration level of 0.1 to 20 weight percent wherein the solution can contain a covalent crosslinking agent which is activated at a minimal temperature of 40°C.
  • the solvent system comprises an organic solvent with or without a polar cosolvent, such as alcohol, amine, or ammonia.
  • the solvent can be an organic liquid which is capable of dissolving the polymeric backbone.
  • a cosolvent may be needed to break up associated domains resulting from aggrega ⁇ tion of ionic species.
  • the polymeric films of the instant invention are formed from a compatible mixture of a ionically and covalently crosslinked sulfon ⁇ ated elastomeric polymer and an amine terminated polycaprolactone.
  • the ionically and covalently crosslinked sulfonated polymers may be in the free acid form or they can be neutralized salts with metals capable of coordinating amino groups or the sulfonated groups are complexed with a metal ion which is capable of coordinating with the amino group of the polycaprolactone polymer.
  • the ionically and covalently crosslinked neutralized, sulfon ⁇ ated polymers of this present invention are derived from elastomeric polymers wherein the elastomeric polymers are derived from unsaturated polymers which include low unsaturated elastomeric polymers, such as butyl rubbers or EPDM terpolymers.
  • unsaturated polymers are selected from the group consisting of partially hydrogenated polyisoprenes, partial ⁇ ly hydrogenated polybutadienes, Neoprene, styrene-butadiene copolymers or isoprene-styrene random copolymers.
  • butyl rubber as employed in the specifica ⁇ tion and claims is intended to include copolymers made from a poly ⁇ merization reaction mixture having therein from 70 to 99.5 by weight of an isoolefin which has about 4 to 7 carbon atoms, e.g., iso- butylene, and about 0.5 to 30% by weight of a conjugated multiolefin having from about 4 to 14 carbon atoms, e.g., isoprene.
  • the resulting copolymer contains 85% to 99.8% by weight of combined isoolefin and 0.2% to 15% of combined multiolefin.
  • Butyl rubber generally has a Staudinger molecular weight as measured by GPC of about 20,000 to about 500,000, preferably about 25,000 to about 400,000, especially about 100,000 to about 400,000 and a Wijs Iodine No. of about 0.5 to 50, preferably 1 to 15.
  • the Butyl rubber may have incorporated therein from about 0.2% to 1.0% of combined multiolefin, preferably about 0.5% to about 6%, more preferably about 1% to about 4%, e.g., 2%.
  • butyl rubber Illustrative of such a Butyl rubber is Exxon Butyl 365 (Exxon Chemical Company) , having a mole percent unsaturation of about 2.0% and a Mooney viscosity (ML, 1 + 3, 212°F) of about 40-50.
  • Butyl rubbers i.e., Butyl rubbers having a viscosity average molecular weight of about 5,000 to 85,000 and a mole percent unsaturation of about 1% to about 5% may be sul ⁇ fonated to produce the polymers useful in this invention.
  • these polymers Preferably, these polymers have a viscosity average molecular weight of about 25,000 to about 60,000.
  • the EPDM terpolymers are low unsaturated polymers having about 1 to about 10.0 weight percent olefinic unsaturation, more preferably about 2 to about 8, most preferably about 3 to 7, defined according to the definition as found in ASTM-D-1418-64 and is intended to mean terpolymers containing ethylene and propylene in the backbone and a diene in the side chain.
  • the preferred polymers contain about 40 to about 75 weight percent ethylene and about 1 to about 10 weight percent of a diene monomer, the balance of the polymer being propylene.
  • the polymer contains about 45 to about 70 weight percent ethylene, e.g., 50 weight percent, and about 2.6 to about 8.0 weight percent diene monomer, e.g., 50 weight percent.
  • the diene monomer is preferably a nonconjugated diene.
  • EPDM terpolymer
  • 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl-2- norbornene, and methyl tetrahydroindene are 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl-2- norbornene, and methyl tetrahydroindene.
  • a typical EPDM is Vistalon 2504 (Exxon Chemical Company) , a terpol mer having a Mooney viscosity (ML, 1 + 8, 212 ⁇ F) of about 40 and having an ethylene content of about 50 weight percent and a 5-ethylidene-2-norbornene content of about 5.0 weight percent.
  • the Mn as measured by GPC of Vistalon 2504 is about 47,000, the Mv as measured by GPC is about 145,000 and the M as measured by GPC is about 174,000.
  • Another EPDM terpolymer, Vistalon 2504-20 is derived from Vistalon 2504 (Exxon Chemical Company) by a controlled extrusion process, wherein the resultant Mooney viscosity at 212 ⁇ F is about 20.
  • the Mn as measured by GPC of Vistalon 2504-20 is about 26,000, the Mv as measured by GPC is about 90,000 and the Mw as measured by GPC is about 125,000.
  • Nordel 1320 (DuPont) is another terpolymer having a Mooney viscosity at 212 ⁇ F of about 25 and having about 53 weight percent of ethylene, about 3.5 weight percent of 1,4-hexadiene and about 43.5 weight percent of propylene.
  • the EPDM terpolymers of this invention have a number average molecular weight (Mn) as measured by GPC of about 10,000 to about 200,000, more preferably of about 15,000 to about 100,000, most preferably of about 20,000 to about 60,000.
  • Mn number average molecular weight
  • the Mooney viscosity (ML, 1 + 8, 212'F) of the EPDM terpolymer is about 5 to about 60, more preferably about 10 to about 50, most preferably about 15 to about 40.
  • the Mv as measured by GPC of the EPDM terpolymer is preferably below about 350,000 and more preferably below about 300,000.
  • the Mw as measured by GPC of the EPDM terpolymer is preferably below about 500,000 and more preferably below about 350,000.
  • the polymer is dissolved in a nonreactive solvent, such as a chlorinated aliphatic solvent, chlori ⁇ nated aromatic hydrocarbon, an aromatic hydrocarbon, or an aliphatic hydrocarbon, such as carbon tetrachloride, dichloroethane, chloro- benzene, benzene, toluene, xylene, cyclohexane, pentane, isopentane, hexane, isohexane or heptane.
  • a nonreactive solvent such as a chlorinated aliphatic solvent, chlori ⁇ nated aromatic hydrocarbon, an aromatic hydrocarbon, or an aliphatic hydrocarbon, such as carbon tetrachloride, dichloroethane, chloro- benzene, benzene, toluene, xylene, cyclohexane, pentane, isopentane, hexane, isohexane or heptan
  • a sulfonating agent is added to the solution of the elastomeric polymer and nonreactive solvent at a temperature of about -100 ⁇ C to about 100°C for a period of time of about 1 to about 60 minutes, most preferably at room temperature for about 5 to about 45 minutes; and most preferably about 15 to about 30.
  • These sulfonating agents are selected from an acyl sulfate, a mixture of sulfuric acid and an acid anhydride or a complex of a sulfur trioxide donor and a Lewis base containing oxygen, sulfur or phos ⁇ phorous.
  • Typical sulfur trioxide donors are SO3, chlorosulfonic acid, fluorosulfonic acid, sulfuric acid, oleum, etc.
  • Typical Lewis bases are dioxane, tetrahydrofuran, tetrahydrothiophene or triethyl phos ⁇ phate.
  • the most preferred sulfonation agent for this invention is an acyl sulfate selected from the group consisting essentially of benzoyl, acetyl, propionyl or butyryl sulfate.
  • the acyl sulfate can be formed in situ in the reaction medium or pregenerated before its addition to the reaction medium in a chlorinated aliphatic or aromatic hydrocarbon.
  • the reaction is quenched with an aliphatic alcohol, such as methanol, ethanol or isopropanol, with an aromatic hydroxyl compound, such as phenol, a cycloaliphatic alcohol, such as cyclohexanol, or with water.
  • the unneutralized sulfonated elastomeric polymer has about 10 to about 200 meq. unneutralized sulfonate groups per 100 grams of sulfonated polymer, more preferably about 15 to about 100, and most preferably about 20 to about 80. The meq.
  • the unneutralized sulfonated polymer is gel free and hydro- lytically stable.
  • Gel is measured by stirring a given weight of polymer in a solvent comprised of 95 toluene-5-methanol at a concen ⁇ tration of 5 weight percent for 24 hours, allowing the mixture to settle, withdrawing a weighed sample of the supernatant solution and evaporating to dryness.
  • Hydrolytically stable means that the acid function, in this case the sulfonic acid, will not be eliminated under neutral or slightly basic conditions to a neutral moiety which is incapable of being converted to highly ionic functionality.
  • Neutralization of the unneutralized sulfonated polymer can be accomplished by the addition of a solution of a polycaprolactone polymer typically dissolved in the mixture of the aliphatic alcohol and nonreactive solvent.
  • the polycaprolactone polymer is dissolved in a solvent system consisting of toluene, optionally containing an aliphatic alcohol.
  • These polycaprolactone polymers are formed by the reaction of e-caprolactone with an organic diamine in the presence of a catalyst as described in U.S. Patent No. 4,421,898.
  • the anhydrous e-caprolactone and the organic diamine in the presence of the catalyst are reacted together in a reaction vessel in the absence of a solvent at a temperature of about 50 to about 200 ⁇ C, more preferably about 75 to about 180 * C and most preferably about 90 to about 100°C for a sufficient period of time to effect polymerization.
  • n - 1 to 500; m - 1 to 20; Rj or R2 are selected from the group consisting of alkyl and cycloalkyl groups having about 1 to about 20 carbon atoms, more preferably about 1 to about 12 carbon atoms, and aryl groups;
  • R3 is selected from the group consisting of hydrogen, alkyl and cycloalkyl groups having about 1 to about 20 carbon atoms, more preferably about 1 to about 12, and aryl groups; and
  • R4 and R5 are hydrogen, alkyl, cycloalkyl or aryl groups.
  • Typical but nonlimiting examples, of useful diamines are:
  • Catalysts useful in the promotion of the above-identified reaction are selected from the group consisting of stannous octanoate, stannous hexanoate, stannous oxalate, tetrabutyl titanate, a variety of metal organic based catalysts, acid catalysts and amine catalysts, as described on page 266 and forwarded in a book chapter authored by R. D. Lundberg and E. F. Cox entitled Kinetics and Mechanisms of Polymerization: Ring Opening Polymerization, edited by Frisch and Rugen, published by Marcell Dekker in 1969, wherein stannous octanoate is an especially preferred catalyst.
  • the catalyst is added to the reaction mixture at a concentration level of about 100 to about 10,000 parts of catalyst per one million parts of e-caprolactone.
  • the resultant polycaprolactone polymer has an Mn as measured by GPC of about 200 to about 50,000, more preferably about 500 to about 40,000, and most preferably about 700 to about 30,000, and a melting point from below room temperature to about 55 * C, more prefer ⁇ ably about 20*C to about 52 ⁇ C, and most preferably about 20 ⁇ C to about 50 ⁇ C.
  • the metal sulfonate-containing polymers at the higher sul ⁇ fonate levels possess extremely high melt viscosities and are thereby difficult to process.
  • a preferential plasticizer selected from the group consisting of carboxylic acids having about 5 to about 30 carbon atoms, more preferably about 8 to about 22 carbon atoms, or basic slats of these carboxylic acids, wherein the metal ion of the basic salt is selected from the group consisting of aluminum, ammonium, lead or Groups IA, IIA, IB and IIB of the Periodic Table of Elements and mixtures thereof.
  • the carboxylic acids are selected from the group consisting of lauric, myristic, plamitic or stearic acids and mixtures thereof, e.g., zinc stearate, magnesium stearate or zinc laurate.
  • the preferential plasticizer is incorporated into the neu ⁇ tralized sulfonated polymer at less than about 60 parts by weight per 100 parts of the sulfonated polymer, more preferably at about 5 to about 40, and most preferably about 7 to about 25.
  • other preferential plasticizers are selected from ureas, thioureas, amines, amides, ammonium and amine slats of carboxylic acids and mixtures thereof.
  • the preferred plasticizers are selected from fatty acid or -metallic slats of fatty acid and mixtures thereof.
  • the resultant neutralized sulfonated polymer with preferential plasticizer is isolated from the solution by conventional steam stripping and filtration.
  • the biodegradable films or coatings of the instant invention are formed by applying the organic solution of the sulfonated ionomer (e.g., zinc sulfo EPDM with 25 meq. of sulfonate group) and of the amine terminated caprolactone (e.g., poly-e caprolactone 3-dimethyl amino propylamine) over a substrate at ambient temperature or at 10-70 ⁇ C by either dip-coating or spray-coating or with the use of other techniques for thin spreading (such as brushing) .
  • the organic solution can be prepared by mixing a proportionate weight of about 1-10% ZSE-25 with 1-10% poly-e caprolactone 3-dimethyl amino propyl ⁇ amine, both in Solvent A.
  • Solvent A comprises 85-97.5% toluene or other appropriate hydrocarbon and 15-2.5% or other alcohol.
  • the organic solvent is permitted to evaporate with or without the aid of forced drying gas, such as nitrogen gas. This step is called the drying process.
  • the drying gas can be from ambient temperature up to the boiling point of the organic solvent system. Preferably, the temperature of the drying gas is between 20°C and 100"C. The most preferred temperature of the drying gas should be about 70°C for fast evaporation of the organic solvent system.
  • After drying the thickness of the applied film or coating should be about 1 to about 100 micro ⁇ meters. Most preferred, the coating thickness should be about 2 to about 40 micrometers for both performance and economic reasons. To control the thickness of the film or coating the solution of this instant invention is applied at 0.5 to 6 weight percent.
  • the concentration should be about 5 weight percent.
  • the film of this instant invention can be applied in single or multiple layers, depending on the desired film or coating thickness. In any instance the organic solvent system is evaporated after each layer application.
  • the biodegradable polymer film or coating can be applied over the sub ⁇ strate or over a previous coating. In the latter case, such practice can modify or improve the performance of the coated system.
  • the polymeric coatings of the instant invention are formed by applying the organic solution of the sulfonated polymer and amine terminated polycaprolactone and optionally the covalent crosslinking agent over the substrate at an ambient temperature of 10-70°C, but at a temperature lower than the activation temperature of the covalent crosslinking agent, by either dip coating or spray-coating or with the sue of other techniques for thin spreading (such as brushing) .
  • the organic solvent system is then permitted to evaporate with or without aid of forced drying gas, such as air or nitrogen gas. This step is called the drying process.
  • the drying gas temperature can be from ambient temperature up to the boiling point of the organic solvent system.
  • the temperature of the drying gas is between 20"C to 100"C.
  • the most preferred temperature of the drying gas should be about 70"C for fast evaporation of the organic solvent system.
  • the thickness of the applied coating should be about 1 micro ⁇ meter to about 100 micrometers. Most preferred, the coating thickness should be about 2 to about 40 micrometers for both performance and economic reasons.
  • the solution concentration of the sulfonated polymer and amine ter ⁇ minated polycaprolactone is applied at 0.5 to 10 weight percent. Most preferably, the concentration should be about 1 to about 5 weight percent.
  • the coating solution of the sulfonated polymer and amine terminated polycaprolactone can be applied in single or multiple layers, depending on the desired coating thickness. In any instance, the organic solvent system is evaporated after each layer application.
  • the sulfonated polymer and amine terminated polycaprolactone coating can be applied over the substrate of interest or over a previous coating. In the latter case, such practice can modify or improve the performance of the coated system.
  • Covalent crosslinking of the above mentioned polymers can be carried out with a variety of common vulcanization formulations involving crosslinking peroxides, carriers for crosslinking peroxides, accelerators and sensitizers.
  • peroxide crosslinking agents include acetyl cyclohexane sulphonyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, bis(4-tert butyl cyclohexyl) peroxydicarbonate, di-cyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-n-butyl peroxydi ⁇ carbonate, dicetyl peroxydicarbonate, disecbutyl peroxydicarbonate, di-isopropyl peroxydicarbonate, tert butyl peroxyeodecanoate, bis (2,4-dichlorobenzoyl) peroxide, tert butyl peroxy pivalate, bis (ortho-methyl benzene) peroxide, bis (ortho-methyl benzoyl) peroxide, bis (3,5,5-trimethyl hexanoyl) peroxide, d
  • Possible carriers for the peroxide are contemplated to the calcium carbonate, clay, EVA copolymer masterbatch, EPDM-masterbatch, silicone oil, plasticizer as well as organic solvents.
  • Accelerators are contemplated to include thiazoles, sulfin- amides, thiurams, dithiocarbamates, guanidines and thioureas,
  • Sensitizers are contemplated to include trialkyl cyanurate, trialkyl isocyanurate, trimethylolpropane trimethacrylate, ethylene glycol di ethacrylate.
  • the concentration of the covalent crosslinking agent in the organic solution or carrier is about 0.1 to about 20 weight percent, more preferably about 0.15 to about 15 weight percent and most prefer ⁇ ably about 0.17 to about 10 weight percent.
  • the coating is first dried in the aforementioned drying step of the process.
  • the dried sulfonated polymer and amine terminated polycaprolactone coating is cured by exposure to an electron beam radiation at ambient tempera ⁇ ture for a sufficient period of time (10 to 60 minutes) to cause covalent crosslinking, wherein the electron beam is 1 to 50 MRad, preferably 2 to 25, and most preferably 5 to 20.
  • the substrate particles coated with dried sulfonated polymer and amine terminated polycaprolactone coating is covalently crosslinked by exposing the coated particles to a saturated vapor or sulfur monochloride at ambient temperature for a sufficient period of time, 1 hour to 48 hours, more preferably 2 to 36, and most preferably 10 to 30, to cause covalently crosslinking.
  • the coated polymer particles may be exposed to vapor by placing them on a screen in a desiccator or in a packed column and exposing the particles to the vapor for a period of time sufficient to cause covalent crosslinking of the sulfonated polymer.
  • the coated particles may be covalently crosslinked by contact with a solution of sulfur monochloride in an organic solvent selected from the group consisting of aliphatic, aromatic and halogenated hydrocarbons.
  • the concentra ⁇ tion of sulfur monochloride in the solution should be about 1 to about 50 weight percent, more preferably 2 to 40 weight percent.
  • the amount of sulfur monochloride solution used to cross-link the polymer con ⁇ tains enough sulfur monochloride to equal about 1.0 to about 20 weight percent of the weight of polymer in the coating, more preferably about 3.0 to about 12 weight percent of the polymer.
  • the solution can be sprayed onto the coated particles by any means which ensures uniform distribution and then the solution is permitted to evaporate.
  • crosslinking with sulfur mono ⁇ chloride may be carried out by direct addition of sulfur monochloride to the sulfonated polymer solution immediately prior to spray coating.
  • the amount of sulfur monochloride added may range from the weight of about 1.0 to about 20 weight percent based on the weight of the sulfonated polymer to which it is added, more preferably about 2.0 to about 15 weight percent and most preferably about 3.0 to about 12 weight percent of the polymer.
  • the spray coating and drying process is then carried out as described above.
  • the ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone coating can be used as a barrier to create desired slow release for many types of fertilizers, micro- nutrients or other solid materials either individually and/or in mixtures, suitable for purposes of the present invention including by way of example: MACRONUTRIENTS
  • Nitrogen for example provided by: Ammonium sulphate Ammonium chloride Ammonium nitrate Diammoniu phosphate Ammonium phosphate nitrate Monoammonium phosphate Ammonium phosphate sulphate Sodium nitrate Potassium nitrate Calcium nitrate Urea Ammonium nitrate-calcium carbonate mixture
  • Potassium for example provided by: Potassium nitrate Sulphate of potash Muriate of potash Potassium metaphosphate
  • Phosphorous for example provided by: Ammonium phosphate nitrate Ammonium phosphate sulphate Monoammonium phosphate Diammonium phosphate Single superphosphate Triple superphosphate Potassium metaphosphate
  • Sulfur for example provided by: Ammonium sulphate Ammonium phosphate sulphate Sulphate potash Calcium sulfate Ammonium bisulphite Ammonium phosphate
  • Calcium for example provided by: Calcium nitrate Calcium sulfate Calcium chloride
  • Borax sodium tetraborate decahydrate
  • Sodium tetraborate-pentaborate Colemanite
  • Conventional slow release fertilizers may also be coated with the crosslinked interpolymer complex polymers in accordance with the present invention, such as:
  • Urease or nitrification inhibitors can be included with the fertilizers.
  • examples of such inhibitors include urease inhibitors such as pheyl phosphoro-diamidate (PPD) and N-(n-butyl) thiophosphoric triamide (NBPT) and nitrification inhibitors such as N-serve (2- chloro-6-trichloro-methyl pyridine) and dicyandiamide (DCD) .
  • PPD pheyl phosphoro-diamidate
  • NBPT N-(n-butyl) thiophosphoric triamide
  • nitrification inhibitors such as N-serve (2- chloro-6-trichloro-methyl pyridine) and dicyandiamide (DCD) .
  • the present invention is particularly suitable for combina ⁇ tions of the aforementioned fertilizers with any pesticide although the present invention can be practiced with fertilizers and/or pesti ⁇ cides alone.
  • suitable pesticides include herbicides such as triallate and trifluralin, insecticides such as carbofuran and aldicarb, fungicides such as captan and benonyl, rodenticides such as 0-ethyl s,s-dipropyl phosphorodithioate-warfavin and chlorophacinone, and nematocides such as o,o-dieth lk o-(p-methylsulfinyl) phenyl phosphonate, ascaricides such as kelthane and plictran, and bacterio- cides such as treyptomycin and terromycin.
  • herbicides such as triallate and trifluralin
  • insecticides such as carbofuran and aldicarb
  • fungicides such as captan and benonyl
  • rodenticides such as 0-ethyl s,s-dipropyl phosphorodithioate-warfavin and
  • the plant growth media to which the fertilizers and ferti ⁇ lizer-pesticide composites coated in accordance with the present invention may be applied include liquid cultures i.e., hydroponics, soil-less cultures and any mixture of sand, vermiculite, peat, perlite, or any other inert or relatively inert support, and soils which can be either irrigated or rainfed soils.
  • the seeds or plants envisioned to be fertilized by the instant invention includes any species falling in the Plant Kingdom. Examples of such include the following: cereals such as wheat, maize (corn), rice, barley, oats; grasses such as bluegrass, fescues, bromegrass for forage, seed and/or turf production; legumes such as alfalfa, soybeans, beans, peas, lentils; oilseeds such as canola, palm, cotton, olive, flax; vegetables such as potatoes, lettuce, celery, carrot, onion, tomatoes, peppers; other broad leaf plants such as mint; coniferous and deciduous trees and shrubs and flowers such as chrysanthemum, roses and tulips.
  • cereals such as wheat, maize (corn), rice, barley, oats
  • grasses such as bluegrass, fescues, bromegrass for forage, seed and/or turf production
  • legumes such as alfalfa, soybeans, beans, peas, lentils
  • herbicides with fertilizers coated with- ionically and covalently crosslinked sulfonated polymers and amine terminated polycaprolactone are not inconsistent with the term vegetation enhancement agent which is intended to be applied to the desired or target plant.
  • the fact that herbicide may kill undesired vegetation does not diminish its role as a vegetation enhancement agent for others, particularly the vegetation for which the fertilizer is intended.
  • the previously listed fertilizers and pesticides either individually and/or in mixtures, may be coated with ionically and covalently crosslinked sulfonated polymers in accordance with the present invention.
  • the substrate of the vegetation enhancement agent for purposes of the present invention may be a member selected from the group consisting of macronutrients, micro ⁇ nutrients, nitrogen fertilizers including inhibitors of urease, nitrogen fertilizers including inhibitors of nitrification activity, slow release fertilizers, and pesticides, in addition to mixtures of a plurality of each of the macronutrients, micronutrients, nitrogen fertilizers including inhibitors of urease, nitrogen fertilizers including inhibitors of nitrification activity, slow release ferti ⁇ lizers and pesticides, as well as mixtures of members from each group of macronutrients, micronutrients, nitrogen fertilizers including inhibitors of urease, nitrogen fertilizers including inhibitors of nitrification activity, slow release fertilizers and pesticides.
  • the fertilizers and fertilizer/pesticide combinations coated with ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone in accordance with the present invention may be mixed with non-coated fertilizers and/or pesticides of the same or different composition.
  • the non-coated member may be selected from the group consisting of macronutrients, micro ⁇ nutrients, nitrogen fertilizers including inhibitors of urease, nitrogen fertilizers including inhibitors of nitrification activity, slow release fertilizers and pesticides in addition to mixtures of a plurality of each of the groups of vegetable enhancement agents as well as mixtures of one or more members of each of the previously mentioned groups.
  • the fertilizer or ferti ⁇ lizer/pesticide combination coated with the ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone in accordance with the present invention may comprise 5 to 95% by total weight of the mixture or the non-coated vegetation enhancement agent may comprise 5 to 95% by total weight of the mixture.
  • the plant growth media to which the fertilizers and fertilizer-pesticide composites coated in accordance with the present invention may be applied include liquid cultures i.e., hydroponics, soil-less cultures and any mixture of sand, vermiculite, peat, perlite, or any other inert or relatively inert support, and soils which can be either irrigated or rainfed soils.
  • substrates which are discrete particulate solids may be encapsulated to form advantageous products.
  • substrates are required to be released in a slow or controlled manner in given environments. Examples include: fertilizers, micro ⁇ nutrients, coated seeds, synthetic reagents or catalysts, pharma ⁇ ceutical and drugs.
  • Substrates can also be modified by encapsulation in cases where their solid surfaces need to be more compatible when they are added to other materials. Examples are engineering plastics, adhesives or rubbers with incorporated filler particles, such as ground lime, carbon black, titanium dioxide, or zinc oxide.
  • the vegetation enhancement agent i.e., fertilizer or fertilizer/pesticide combination, to which the present invention is applicable is preferably in a substantially solid form, i.e., particles, having a dimension, and preferably a major dimension, within the range of about 1.0 to 10.0 mm.
  • the fertilizer particles are granules having a diameter within the range of about 1.0 to 6.0 mm and most preferably about 1.0 to about 3.5 mm.
  • Commercial fertilizer granules typically have a diameter of about 2.3 mm, although particles, such as granules having a diameter as large as about 6 mm, have been found to be useful, particularly for purposes of aerial application, for example used in the forestry industry.
  • the present invention has been described in con ⁇ nection with coating a vegetation enhancement agent, such as fertilizers/pesticide combinations, with a layer or film of car- boxylated polymer, it should be understood that the present invention may also be used to coat a previously coated fertilizer or fertilizer/pesticide combination, such as conventional slow release fertilizers.
  • fertilizers coated with covalently crosslinked sulfonated polymer and amine terminated caprolactone in accordance with the present invention may also be coated with a conventional slow release coating, to which additional applications of the covalently crosslinked sulfonated polymer and amine terminated polycaprolactone films or coatings in accordance with the present invention may be applied.
  • a multiple-coated fertilizer or fertilizer/pesticide combination may be produced in accordance with the present invention.
  • the film or coating of the covalently crosslinked sulfonated polymer and amine terminated polycaprolactone be either in direct contact with the vegetation enhancement agent, or form the exterior surface of the coated composite.
  • the present invention is also directed to agricultural processes, such as those for the enhancement of vegetation or vegetable matter.
  • vegetable matter is meant to be a division of nature comprising the plant kingdom as distinguished from matter of animal and mineral origin.
  • vegetable matter includes seeds and plants, including seedlings, young plants, or any organ from which a plant can be generated, including naturally promulgated vegetable matter in addition to genetically engineered vegetable matter.
  • the process of the present invention is directed to the stimulation of the germination and growth of a seed or a plant, including seedlings, young plants or any organ from which a plant can be generated, which involves the step of exposing the vegetable matter, e.g., the seed or plant, and/or the plant growth medium, i.e., soil, water and the like, either before, simultaneously with, or after the addition of the seed or plant to the plant growth medium to a fertilizer and/or fertilizer-pesticide combinations having a thin layer of a carboxylated polymer coated thereon.
  • the vegetable matter e.g., the seed or plant
  • the plant growth medium i.e., soil, water and the like
  • the process also relates to the intimate admix ⁇ ing of fertilize, such as urea, ammonical, phosphorus and/or sulphur fertilizers, alone or combined with pesticides, with a seed or plant, or other vegetable matter, as defined herein, without damage to the same in a plant growth medium which involves the steps of: 1) admixing or otherwise contacting a fertilizer, preferably in solid granular form, having a thin ionically and covalently cross ⁇ linked sulfonated polymer and amine terminated polycaprolactone film or coating thereon with a seed or plant;
  • fertilizers with thin films or coatings of ionically and covalently crosslinked sul ⁇ fonated polymers and amine terminated polycaprolactones for example urea and ammonium sulfate can be placed with the seed at the rate exceeding 25kgN/ha without damage to the seed, seedlings, or young plants.
  • the fertilizer and fertilizer/pesticide combinations having thin films or coatings of ionically and covalently sulfonated polymer and amine terminated polycaprolactone have been found to be extremely effective in stimulating seedling emergence and early plant growth by permitting the placement of urea fertilizers with the seed at the time of planting.
  • the thin ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone film or coating slows the release of urea and ammonium to a sufficient extent to prevent burning of the seed or young seedling to which such a fertilizer is applied.
  • urea coated with a thin film of ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone in accordance with the present invention can be applied to the plant growth media at a rate in excess of 25kgN/ha without raising the pH of the seed in the plant media a sufficient extent to burn the seed and prevent emergence.
  • fertilizers coated in accordance with the present invention may also preferably contain a source of sulfur and phosphorous, in which case, the fertilizer may be applied so as to supply nitrogen at a rate in excess of 25kg/ha, sulfur in excess of 15kg/ha, and phosphorous at a rate in excess of 30kg ha without burning the seeds or preventing subsequent emergence of the seedlings.
  • the present invention is particularly suitable for replacing split or multiple applications of uncoated fertilizers to ensure that the available plant nutrient matches the physiological need of the crop for the same.
  • plants do not require all of their nitrogen at one time; for example, wheat requires over 35% of its nitrogen between booting and the soft touch stage.
  • uncoated fertilizers are applied in split applications at key physiological plant growth stages such as tillering, stem elonga ⁇ tion, booting and seed filling to ensure that the nitrogen is avail ⁇ able to the plant as required.
  • Controlled release nitrogen there ⁇ fore, is effective in replacing split fertilizer applications. Controlled release nitrogen holds the nitrogen in a form until the nitrogen is needed by the plant.
  • the sulfonated polymer coated fertilizer and fertilizer/pesticide combina ⁇ tions in accordance with the present invention are particularly suitable for introduction with the seed and/or into the plant growth median during a single agricultural step so as to eliminate the need for post emergence application of the fertilizer.
  • the fertilizer and fertilizer/pesticide combination coated with thin films of ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone in accordance with the present invention may also be introduced into the soil prior to a subsequent planting of the seeds.
  • the coated fertilizer of the present invention may be introduced into the soil in the Fall of a year prior to planting wheat in the Spring of the following year, without appreciable loss of nutrients.
  • the coated fertilize of the present invention may be formulated so as to supply nitrogen at a sufficient rate and timing of release to satisfy the physiological need for nitrogen of the wheat beginning in the Spring of the year when the wheat is sown through the growing season.
  • the coated fertilizer of the present invention may also be applied in a single application to supply nitrogen at a rate and timing of release essentially the same as provided by separate applications of fertilizer prescribed under a standard intensive cereal management program (ICM) thereby eliminating the need for multiple fertilizer applications which would otherwise be required by such an ICM program.
  • ICM intensive cereal management program
  • fertilizers and fertilizer/pesticide combinations with thin films or coatings of ionically and covalently crosslinked sulfonated polymer and amine terminated polycaprolactone permits the fertilizer to be applied to the soil at a rate which is at least 10% less than a fertilization rate for a fertilizer not coated in accordance with the present invention determined by a standard soil testing method as being required for the particular crop in the soil of the particular region.
  • the rate of fertilizer reduction may be as much as about 50% less than the fertilization rate otherwise required, typically the rate is reduced within the range of about 10-20% less than a conven ⁇ tional fertilization rate.
  • fertilizers and fertilizer/pesti ⁇ cide combinations coated with thin films of ionically and covalently crosslinked sulfonated polymers and amine terminated polycaprolactone experience reduced nitrogen losses. This is particularly true for urea and ammonium sulfate.
  • nitrogenous fertilizers added to moist soils i.e., soils where the moisture levels exceed 2/3 of field capacity, i.e., 22kPa, are subject to a loss of nitrogen due to a variety of factors including: leaching into ground waters, the denitrification to N2O and/or N2 gas, volatilization of ammonia gas, and immobilization into the active microbial biomass.
  • fertilizers coated with thin films of ionically and covalently crosslinked sulfonated polymers and amine terminated polycaprolactones in accordance with the present invention experience substantially reduced losses of nitrogen by controlling the release of nitrogen by the coated fertilizer; thus, the amount of fertilizer nitrogen available at any particular time which would be subjected to the previously mentioned deleterious effects is minimized.
  • An advan ⁇ tage of the present invention therefore, is a reduction in the losses of, for example, ammonical nitrogen by chemical, physical and bio ⁇ logical occurrences.
  • the present invention has been found effective in increasing plant yields because more nitrogen is avail ⁇ able for the needs of the plant, while decreasing pollution of ground water with fertilizer-derived nitrates, decreasing destruction of the ozone layer of the atmosphere due to fertilizer-derived N2O, and increasing residual nitrogen to benefit subsequent crops planted during the normal course of agricultural rotation.
  • Polymer coating system B also contains 2 weight percent of zinc sulfo EPDM (ZSE-25) and poly-e-caprolactone 3-dimethyl amino propylamine, but with the molecular weight of the latter of about 6,000; also at similar 9/1 ratio of the former to the latter.
  • urea slides were coated for immersion tests. The procedures for preparing coated samples of urea slides and conducting immersion tests are described below.
  • Urea samples were prepared by depositing reagent grade urea (Fisher Scientific) over microscope glass slides. This was done by dipping glass slides into molten urea at a temperature of about 135-145*C, followed by cooling and solidification of the urea layer. The urea layer was built up to about 7 mm by four to five successive dipping and cooling cycles. These urea samples were then coated by a polymeric film using a second dipping procedure. Urea slides were repeatedly dipped into polymer solutions, such as those described above, followed by drying in a vacuum oven at 70°C for ab ⁇ ut 3 hours. The dipping and drying cycles were repeated until the film thicknesses shown in Table I were obtained.
  • the barrier properties of the various polymeric films were determined by immersion of each coated urea slide in about 100 g of deionized water at room temperature. The amount of urea released into the water was determined by recovering the urea after evaporating the water. Each sample was initially immersed for 1 day, followed by immersion in fresh water for 3 days and for weekly intervals there ⁇ after.
  • Table I shows the permeabilities of urea solution extracted from the coated slides which were immersed in water at room tempera ⁇ ture.
  • the permeabilities of the coating materials were determined by applying Fick's law of diffusion at steady state. Pick's law states that:
  • J - mass flux (loss) through the film or membrane A - trans ⁇ port area, ⁇ C - concentration gradient, 8 - film or membrane thickness and D - membrane diffusivity constant which is equal to the ratio of permeability (P) over the solubility ratio (K) of urea in the membrane and in water.
  • the performance of the ionomer coatings was compared with that of two commercially used coating materials.
  • the first commercial coating solution was a tung oil solution made by Formby of Mississippi at 30 weight percent solids in petroleum distillate.
  • the second commercial coating solution was linseed oil modified polyurethane Type I made by Minwax Paint Co. of New Jersey at 45% solids in petroleum distillate.
  • the two commercial coatings were cured at 70°C for 48 hours after coating.
  • the permeability of urea solution through the ionomer films was found to be about 2 orders of magnitude lower than either that of tung oil or that of polyurethane. Tung oil and polyurethane were disclosed as release control coatings for water soluble fertilizers in U.S. Patent Nos. 3,321,298 and 3,233,518.
  • This Example shows that encapsulated urea having a coating of the instant invention is more resistant to water extraction than the urea encapsulated by commercially used coatings.
  • the SEPDM and polycaprolactone coated fertilizer granules are produced using the following procedure:
  • 4 kg of 2 to 3 mm fertilizer granules are introduced into a fluid bed coating machine, including a Wurster insert, manufactured by Glatt Air Techniques Inc., model number GPCG-5.
  • the fertilizer is fluidized by blowing 130 scfm of heated air (45 ⁇ C) through bed. After the bed reaches a temperature of 30 ⁇ C, a 1.25 weight percent solution of the SEPDM polymer containing N,N-dimethyl-l, 3-propane diamine terminated polycaprolactone in toluene and methanol cosolvent is sprayed onto the fertilizer granules at the Wurster insert entrance.
  • the spray nozzle uses a commercial two fluid nozzle using air at 3 bars pressure to form an atomized spray regime in the Wurster insert.
  • the spraying is continued at 40 gm/min rate until the required thickness of polymeric coating is built up on the fertilizer, i.e. approximately 80 minutes per a coating level of 1 wt% polymer on the fertilizer.
  • the thus coated granules are blown by the heated air upwards into they drying section of the machine.
  • the solvents are evaporated by the hot stream, leaving a thin coat of dried polymeric material on the granules.
  • the dried granules fall back into the fluid bed and then re-enter the Wurster insert where the coating process is repeated.
  • multiple films or layers of the polymeric coating is built up until the spraying was stopped.
  • the spraying is continued until 2 wt% of polymer is added.
  • the spraying is stopped and the coated granules are dried with the hot air for 5 minutes.
  • the contemplated method for crosslinking the polymer using electron beams is as follows:
  • Granular fertilizer pellets in the size range of 2 to 3 mm coated with 2 wt.% per zinc sulfonated EPDM and amine terminated polycaprolactone is placed in a monolayer on a flat bed cart.
  • the cart is placed in an electron beam generator until a dose of 10 Megarads is obtained.
  • coated pellets consisting of 2 wt.% zinc sulfonated EPDM terpolymer and N-N dimethyl-1, 3-propane diamine terminated polycaprolactone on 2-3 mm granular fertilizer are placed in a monolayer in a flat dish. The dish is then put into a desiccator which contains a separate is which contained sulfur monochloride. The desiccator is closed and evacuated so that only sulfur monochloride vapor remains. The pellets were left in the desiccator for 24 hours. After that they are removed and placed in a vacuum oven at 40"C for 10 to 12 hours in order to remove residual sulfur monochloride.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Fertilizers (AREA)
  • Polyamides (AREA)

Abstract

On décrit un engrais encapsulé soluble dans l'eau, qui comprend une couche polymère de 2 à 100 micromètres environ, recouvrant la surface dudit engrais, ladite couche polymère se composant d'un polymère sulfoné à réticulation covalente et comprenant de 10 à 200 meq environ de groupes sulfonés pour 100 grammes dudit polymère sulfoné à réticulation covalente, lesdits groupes sulfonés étant neutralisés par un polymère de polycaprolactone caractérisé par la formule (I) où R1 et R2 représentent un groupe alkyle, cycloalkyle ou aryle; R3, R4 et R5 représentent hydrogène ou des groupes alkyle, cycloalkyle ou aryle; m est équivalent à un nombre compris entre 1 et 20 et n équivaut à un nombre compris entre 1 et 500.
EP9292906040A 1991-03-28 1992-01-03 Ionically and covalently crosslinked biodegradable barrier films of ionomer polymer Withdrawn EP0577627A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67660791A 1991-03-28 1991-03-28
US676607 1996-07-08

Publications (2)

Publication Number Publication Date
EP0577627A1 true EP0577627A1 (fr) 1994-01-12
EP0577627A4 EP0577627A4 (en) 1994-09-14

Family

ID=24715196

Family Applications (1)

Application Number Title Priority Date Filing Date
EP9292906040A Withdrawn EP0577627A4 (en) 1991-03-28 1992-01-03 Ionically and covalently crosslinked biodegradable barrier films of ionomer polymer

Country Status (4)

Country Link
EP (1) EP0577627A4 (fr)
CA (1) CA2104688A1 (fr)
NO (1) NO933437L (fr)
WO (1) WO1992017422A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569118B1 (fr) * 1992-05-04 1999-08-18 Orica Explosives Technology Pty Ltd Nitrate d'ammonium poreux et durci
DE19631320A1 (de) * 1996-08-02 1998-02-05 Bayer Ag In Hydrogelen eingebettetes biologisches Material, ein Verfahren zu dessen Einbettung sowie dessen Verwendung als künstliches Saatgut
ES2184608B1 (es) 2001-04-23 2005-03-16 Enmiendas Y Abonos Organicos S.L. Fertilizantes organicos-minerales complejos.
DK2885261T3 (da) 2012-08-15 2019-08-12 Koch Agronomic Services Llc Flydende sammensætninger, der indeholder ureaseinhibitorer og glycolalkylethere
BR112015003095A2 (pt) * 2012-08-15 2017-07-04 Koch Agronomic Services Llc composições líquidas contendo inibidores de urease e aril-alquila álcoois
US10501383B2 (en) 2014-10-31 2019-12-10 Koch Agronomic Services, Llc Nitrification inhibitor compositions and methods of making thereof
CN114316527A (zh) * 2021-12-27 2022-04-12 江苏金聚合金材料有限公司 一种含氮营养型生物降解改性树脂及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536547A (en) * 1983-12-28 1985-08-20 Exxon Research And Engineering Co. Polymer complexes of a neutralized ionic polymer and a polycaprolactone polymer
US4701204A (en) * 1985-12-12 1987-10-20 Exxon Research And Engineering Company Composite comprising a substrate coated with polymeric complexes
US4988377A (en) * 1986-04-24 1991-01-29 Exxon Research And Engineering Company Coatings with sulfonated polymers
US4741956A (en) * 1986-07-09 1988-05-03 Exxon Research And Engineering Company Biodegradable coatings of ionomer polymer
US5110486A (en) * 1989-12-14 1992-05-05 Exxon Research And Engineering Company Breaker chemical encapsulated with a crosslinked elastomer coating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9217422A1 *

Also Published As

Publication number Publication date
EP0577627A4 (en) 1994-09-14
NO933437L (no) 1993-11-08
NO933437D0 (no) 1993-09-27
WO1992017422A1 (fr) 1992-10-15
CA2104688A1 (fr) 1992-09-29

Similar Documents

Publication Publication Date Title
US5256181A (en) Coatings with ionically and covalently crosslinked sulfonated polymers
US5188654A (en) Coatings with ionically and covalently crosslinked neutralized carboxylated polymers
US5435821A (en) Controlled release vegetation enhancement agents coated with sulfonated polymers, method of production and prcesses of use
EP0357687B1 (fr) Revetements de polymere sulfone pour liberation regulee d'engrais
CN101384523B (zh) 具有改进的尿素酶抑制效果的制剂以及包含它们的含尿素肥料
US5176734A (en) Granular fertilizer with a decomposable coating and process for producing the same
EP0255752B1 (fr) Engrais granulé à revêtement dégradable et son procédé de fabrication
US20030215657A1 (en) Triggered start products and processes for the production and use thereof
US4741956A (en) Biodegradable coatings of ionomer polymer
EP0577627A1 (fr) Couches d'arret biodegradables, a reticulation ionique et covalente, composees d'un polymere ionomere
US4979980A (en) Biodegradable barrier films of ionomer polymer
US5006147A (en) Biodegradable barrier films of ionomer polymer
CA1252643A (fr) Engrais a effet prolonge et liberation programmee des nutriments
EP0344248B1 (fr) Enrobage de pesticides avec des polymères sulfonés
US4997470A (en) Biodegradable barrier films of ionomer polymer
US4788081A (en) Biodegradable coatings of ionomer polymer
CN111601783B (zh) 包衣农业化学品组合物
JPH07206565A (ja) 微量要素含有被覆粒状肥料
KR950007161B1 (ko) 분해성 피막으로 피복된 입상비료
JPH1192261A (ja) 被覆粒状肥料
JP4256620B2 (ja) 被覆粒子、およびそれを含有する配合肥料
NZ754997A (en) Granule composition and process for preparation thereof
AU2019204626A1 (en) Granule composition and process for preparation thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930928

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE DK FR GB IT NL

A4 Supplementary search report drawn up and despatched

Effective date: 19940727

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): BE DE DK FR GB IT NL

17Q First examination report despatched

Effective date: 19950210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19950810