WO2007019148A2 - Compositions moussantes a base d'urethanne destinees a la lutte contre les ravageurs - Google Patents

Compositions moussantes a base d'urethanne destinees a la lutte contre les ravageurs Download PDF

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Publication number
WO2007019148A2
WO2007019148A2 PCT/US2006/029987 US2006029987W WO2007019148A2 WO 2007019148 A2 WO2007019148 A2 WO 2007019148A2 US 2006029987 W US2006029987 W US 2006029987W WO 2007019148 A2 WO2007019148 A2 WO 2007019148A2
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composition
composition according
microencapsulated pesticide
polyol
polyurethane
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PCT/US2006/029987
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English (en)
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WO2007019148A3 (fr
Inventor
Toni Aldridge
Tammy Tornow
Nelson Johnson
Patrick Mulqueen
Ian Tovey
John Silverthorne
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Syngenta Participations Ag
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Publication of WO2007019148A2 publication Critical patent/WO2007019148A2/fr
Publication of WO2007019148A3 publication Critical patent/WO2007019148A3/fr

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    • 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
    • A01N25/16—Foams

Definitions

  • the field of the invention relates to polyurethane flexible foam forming compositions, methods for treating substrates with the compositions and methods for using such compositions to control pests.
  • Baiting is another method to control termites. Bait stations are installed underground around the perimeter of the house, for example, every 10 to 20 feet and 2 feet out from the house. This method takes considerable time to eliminate a colony of up to one year. It relies upon individual termites feeding on the bait which contains a non-repellant termiticide (e.g. hexaflumuron, sulfluramid), and returning to the colony to pass the poison on to other members, killing a portion of the exposed colony. However, termites that are not attracted to the bait may seek out wood in the building to feed on.
  • a non-repellant termiticide e.g. hexaflumuron, sulfluramid
  • the present invention is directed to a curable polyurethane flexible foam forming composition containing a microencapsulated pesticide, flexible foams prepared therefrom, and methods of making the same.
  • the curable polyurethane flexible foam forming composition of the invention is a mixture of one or more components that react to form a polyurethane flexible foam and at least one microencapsulated pesticide, which composition is suitable for application to various substrates.
  • Suitable components that react to form a polyurethane flexible foam include at least one polyisocyanate material, at least one active hydrogen- containing material and at least one blowing agent.
  • the present invention provides a curable, two- part polyurethane flexible foam forming composition adapted to cure under ambient conditions comprising a mixture of (A) at least one polyisocyanate, (B) at least one polyol, (C) at least one blowing agent and (D) at least one microencapsulated pesticide.
  • the foam forming compositions of the invention containing microencapsulated pesticides are usually significantly lower in their acute toxicities to non-targets (e.g. humans) than are non-encapsulated pesticide products thereby allowing easier safe handling of the compositions and incorporation of pesticides without significant operator health concerns. Moreover, the controlled release characteristics of such foam forming compositions containing microencapsulated pesticides allow for greater flexibility in overall product design and polymer selection to achieve the desired pesticide release characteristics.
  • the microencapsulated pesticides can be premixed with the polyisocyanate or with the polyol component or they can be added separately to the reaction mixture as it is being applied to a target substrate.
  • the inventive foaming composition may also contain polymerization catalysts, antimicrobial agents, non-encapsulated pesticides, or other additives such as rheology control agents, plasticizers, thickeners, surfactants, pigments, fillers, dispersants, freeze-thaw stabilizers, flame retardants and coalescents.
  • compositions of the invention are particularly suitable for use in a method for reducing or preventing pest attack or pest infiltration of substrates or loci that are susceptible or vulnerable to such attack or infiltration, which method comprises (I) providing a reaction mixture of at least one microencapsulated pesticide and one or more components that react to form a polyurethane flexible foam (such as at least one polyisocyanate, at least one polyol and at least one blowing agent), (II) applying the mixture to the susceptible substrate or locus; and (III) foaming the mixture under ambient conditions to form a polyurethane flexible foam on the substrate or in the locus.
  • a reaction mixture of at least one microencapsulated pesticide and one or more components that react to form a polyurethane flexible foam such as at least one polyisocyanate, at least one polyol and at least one blowing agent
  • a polyurethane flexible foam such as at least one polyisocyanate, at least one polyol and at least one blowing agent
  • a coating of the foam is formed on a target substrate such as a construction material (e.g., concrete), a plastic vapor barrier or a utility penetration such as a pipe or conduit.
  • a foam is formed in a pest susceptible locus such as a wall void or bath trap.
  • the flexible foaming compositions of the invention can be applied to target substrates and loci by professionals or non-professionals by spraying, painting, rolling, or brushing, before, during, or after construction and may be formulated to provide flexible foams having effectiveness against fungi, wood destroying microorganisms, insects and representatives of the order acarina, including, for example, arthropods such as termites, wood-boring ants, wood-boring insects and spiders.
  • ambient temperature shall be understood to mean a temperature of from about 0 degrees Celsius to about 50 degrees Celsius; or particularly from about 15 degrees Celsius to about 32 degrees Celsius; or more particularly from about 20 degrees Celsius to about 25 degrees Celsius.
  • curing under ambient conditions shall be understood to mean a foam curing reaction that takes place at ambient temperatures without the addition of external heat. As the curing reaction itself is exothermic, it will be understood that the temperature of the reaction mixture per se may temporarily exceed ambient temperatures during curing due to the exothermic nature of the chemical reaction occasioned by the formation of the urethane foam.
  • high-solids shall be understood to mean foaming systems with a solids content exceeding 85 wt %.
  • microencapsulated insecticide is understood to refer to small solid particles or liquid droplets of a compound which has a lethal effect on insects of a type to be controlled (namely that the application of an appropriate amount of such compound results in death of a substantial portion of the insects being treated) coated with a thin film of a polymer coating or shell material.
  • microencapsulated insecticide is used to describe particles with diameters between 0.05 and 1000 ⁇ m.
  • suitable microencapsulated insecticides have and average particle size of from about 1 to 50 ⁇ m.
  • the term "monomer” means a polymerizable molecule that forms a basic repeating unit in a polymer chain.
  • Oligomer refers to a polyfunctional polymerized compound whose backbone is formed from 2 to 10 monomers.
  • Prepolymer refers to a polyfunctional polymerized compound whose backbone is formed from more than 10 monomers, but has a viscosity or can be made to have a viscosity at ambient temperatures that is suitable for foaming.
  • pests includes fungi and other wood decaying microorganisms, insects and representatives of the order acarina, including arthropods such as termites, ants, other wood boring insects and spiders. Specific species of such pests are defined in more detail below.
  • pesticide product refers to the combination of active and inert constituents associated with a microencapsulated pesticide that is used alone or in combination with one or more non-encapsulated pesticides.
  • polyurethane foam or “foam” as used herein refers to cellular products as obtained by reacting polyisocyanates with isocyanate-reactive hydrogen containing compounds, using foaming agents, and in particular includes cellular products obtained with water as reactive foaming agent (involving a reaction of water with isocyanate groups yielding urea linkages and carbon dioxide and producing polyurea-urethane foams) and/or with highly volatile organic substances as non-reactive foaming (blowing) agents, and with active hydrogen-containing materials such as polyols as isocyanate-reactive compounds.
  • the term "flexible” in the context of the present application is defined as is customary in the art and refers to polyurethane foams that show a relatively high resilience.
  • the term “flexible” as used herein in reference to polyurethane foams of the invention refers to a foam having a percent recovery of at least 50%, specifically at least 70% and more specifically 80% in at least one of the three dimensional directions.
  • the percent recovery of suitable foams is measured according to the following protocol: Test equipment
  • Foam of prescribed dimension 50mm x 50mm x 25mm slab of foam cut form a larger slab to exclude external surfaces from the casting process.
  • acceptable flexible foam shows a 10mm indentation with a loading of ⁇ 2kg, often ⁇ lkg.
  • Acceptable products show recovery of foam height to at least 50% of the original indentation depth on removal of pressure, in particular products show recovery to at least 70% and more particularly products show recovery to at least 80%.
  • Brittle, non-flexible foam requires > 2kg, typically 5-25kg to produce a 10mm depression. At these high levels of loading, the foams are seen to be compressed more or less irreversibly due to fracture and/or crushing of the foam structure. These products are deemed unsatisfactory.
  • two-part as used herein in reference to flexible foaming compositions of the invention relates to compositions having at least two parts including (A) a polyisocyante material in a first part, (B) a polyol in a second part, (C) a blowing agent and (D) the above- described microencapsulated pesticide in said first or said second part, or optionally in one or more additional parts as desired (such as a separate pesticide containing part, for example), the two (or more) parts being intended to be mixed together prior to use.
  • polyurethane flexible foams containing microencapsulated pesticides have improved pesticide retention and a concomitant resistance to wood pests such as termites, wood-boring ants, wood-boring insects, spiders, fungi and wood destroying microorganisms.
  • the pest resistant polyurethane flexible foams are prepared from a polyurethane reaction system comprising (i) a mixture of one or more components that react to form a polyurethane flexible foam and (ii) at least one microencapsulated pesticide.
  • the system is suitable for application to various target substrates and loci by applying a layer or layers of such system thereto.
  • Suitable components that react to form a polyurethane flexible foam include at least one polyisocyanate material, at least one active hydrogen-containing material and at least one blowing agent.
  • a two-part, polyurethane flexible foaming composition adapted to cure under ambient conditions which comprises: (A) at least one polyisocyanate, (B) at least one polyol, (C) at least one blowing agent and (D) at least one microencapsulated pesticide.
  • the release rate of pesticides from coated substrates or target loci can be better controlled by applying to a target substrate or locus a flexible foaming composition comprising a mixture of at least one polyisocyanate, at least one polyol, at least one blowing agent and at least one microencapsulated pesticide, which mixture is foamable under ambient conditions to form a microencapsulated pesticide containing polyurethane flexible foam on the substrate or in the locus.
  • the present invention provides a high-solids pesticidal flexible foaming composition
  • a high-solids pesticidal flexible foaming composition comprising a reactive mixture of: (A) at least one polyisocyanate, (B) at least one polyol, (C) at least one blowing agent and (D) a pesticidally effective amount of at least one microencapsulated pesticide, which composition is foamable under ambient conditions and wherein the microencapsulated pesticide within flexible foams prepared therefrom is effective to reduce or prevent pest attack or pest infiltration of the target substrate or locus.
  • any known system for producing polyurethane flexible foams may be used as a starting point for the pesticidal flexible foaming compositions of the invention, such as those set forth in the chapter on Foamed Plastics by Kyung W. Suh. (Section 5.1 Flexible Polyurethane and references cited therein) of the Kirk-Othmer Encyclopedia of Chemical Technology Copyright ⁇ 2002 by John Wiley & Sons, Inc.
  • base formulations will be modified to include a pesticidally effective amount of a microencapsulated pesticide.
  • each of the components are mixed together in a mixing chamber.
  • each of the components is separately introduced into the mixing chamber.
  • each of the components can be introduced as a separate stream into the mixing chambers.
  • any means which is recognized in the art, such as a variable speed pump, can be employed to separately control the flow of each of the components into the mixing chamber in order to provide the desired product.
  • one or more of the components can be premixed prior to introduction into the mixing chamber.
  • the polyols (or polyisocyanates) and a microencapsulated pesticide can be premixed and introduced to the mixing chamber as one component. It is possible to combine all of the ingredients other than the diisocyanate (or polyol) and introduce just two components to the mixing stream. It also is possible to pre- react the diisocyanate with at least a portion of the polyol. The pre-polymer is then introduced to the mixing chamber along with the other components, either singularly or premixed, to produce a flexible foam. Since an extra step is involved, the resulting foam is usually more expensive.
  • the polyurethane flexible foaming system is mixed with a pesticidally effective amount of a suitable microencapsulated pesticide.
  • the microencapsulated pesticide is selected to impart pest resistive properties to the final flexible foam and covered substrate or treated locus as required under the prevailing circumstances.
  • a pre-mix of the microencapsulated pesticide with the polyol, blowing agent, catalyst (if used) and other ingredients (except the polyisocyanate) is prepared which is suitable to package, sell and ship and is suitable for use in a multi-component (e.g., two-part) polyurethane foaming system.
  • microencapsulated pesticide with the active hydrogen (polyol) component and, optionally, other additives such as a blowing agent, catalyst or reaction accelerator in a composition which is substantially free of isocyanate functional compounds.
  • other additives such as a blowing agent, catalyst or reaction accelerator
  • a pre-mix of the microencapsulated pesticide with the polyisocyanate and other ingredients is also within the scope of the invention.
  • a two part system as a co-package or in a dispenser having a static mixer or the like that is suitable for shipping and/or selling which comprises a first pre-mix (A) containing at least one polyisocyanate material which is substantially free of active hydrogen compounds, a second pre-mix (B) containing at least one polyol which is substantially free of isocyanate functional compounds, and wherein at least one of the first or the second pre-mixes contain (C) at least one microencapsulated pesticide.
  • a pesticidally effective amount of the microencapsulated pesticide is present in only one of the pre-mixtures.
  • both pre-mixes in the co-pack contain a portion of the total pesticidally effective amount of the microencapsulated pesticide.
  • the polyisocyanate, polyol and microencapsulated pesticide are provided in separate premixes in a tri-pack configuration.
  • the two pre-mixes are mixed together immediately prior to application (such as by spraying or brushing) to prevent the clogging of the application equipment.
  • the two parts are combined within the nozzle of a pressurized spraying device.
  • suitable spraying devices are suitable for the practice of the present invention. These devices are well understood by those having skill in the art.
  • one spray configuration employs a dispensing gun and associated container pumps actuated by compressed air (e.g., 110 psi).
  • Each container (such as a 55 gal. drum) contains one part of the two-part system, with at least one part containing a microencapsulated pesticide.
  • the dispensing gun cartridge assembly contains a mixing chamber, where the two parts are combined under pressure.
  • the parts are mixed in substantially stochiometric amounts and, in particular, at a 1:1 ratio.
  • suitable spraying devices allow the pre-mixes to be combined within the nozzle by directing at least two liquid feed streams into the spraying nozzle. It will be understood that three liquid feed streams will be provided in systems having a tri-pack configuration.
  • the present invention contemplates a two (or more) part system wherein a first part comprising at least one active hydrogen-containing material is combined with a second part comprising at least one polyisocyanate material to form the pest resistant polyurethane flexible foam, wherein either one or both of the parts contains a microencapsulated pesticide.
  • This may be accomplished simply by applying the two (or more) parts to the target substrate or locus to be protected sequentially; first with the active hydrogen-containing material mixture and then with the second part containing the polyisocyanate material.
  • the combined parts are curable under ambient conditions to form a polyurethane flexible foam containing a pesticidally effective amount of a microencapsulated pesticide. The reaction proceeds readily at ambient temperature and is exothermic.
  • suitable polyurethane formulations will have a viscosity that is acceptable for foaming.
  • the viscosity at ambient temperature be within the range of 100 to 10,000 cP, particularly 500 to 1,000 cP, to provide a foaming composition which penetrates and spreads adequately within a locus or over the surface of a substrate being coated.
  • More viscous compositions may be made less viscous by the addition of compatible solvents (both inert and reactive).
  • suitable inert solvents include fully etherified or esterified glycol ethers, , the acetates, xylene, toluene and methyl isobutyl ketone.
  • Suitable reactive solvents include the lower molecular weight diols such as ethylene glycol, diethylene glycol, 1,4-butane diol, 1,6-hexane diol, and 1,10-decane diol and the lower molecular weight oligomers of ethylene, propylene and butylene glycol, for example, polyethylene glycol 400 or polypropylene glycol 425.
  • the solvents may be present in an amount of up to about 15% by weight and more particularly from about 10 to 15% by weight of the entire composition.
  • compositions are substantially free of added volatile organic solvents (those skilled in the art will appreciate that microencapsulated pesticides used in the foamable compositions of the invention may contain some organic solvent and that this is considered to not be a constituent of added solvent).
  • suitable polyisocyanates include aromatic, aliphatic, and cycloaliphatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate (“MDI”), toluene diisocyanate (“TDI”), xylylene diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, para-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, mixtures thereof, and the like.
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • xylylene diisocyanate tetramethylxylene diisocyanate
  • naphthalene diisocyanate para-phenylene diisocyanate
  • tetramethylene diisocyanate hexamethylene
  • Polymeric polyisocyanates, biurets, blocked polyisocyanates, and mixtures of polyisocyanates with melting point modifiers can also be used.
  • MDI is a particularly preferred polyisocyanate.
  • a suitable commercially available polymeric diphenylmethane diisocyanate is "Rubinate M" polyisocyanate (Huntsman Polyurethanes).
  • the polyol component comprises more than one polymerizable OH (hydroxyl) functional compounds, suitably comprising two or more hydroxyl groups, per molecule on average.
  • the polymerizable, hydroxyl functional compounds may be aliphatic and/or aromatic.
  • the polymerizable, hydroxyl functional compounds may be straight, cyclical, fused, and/or branched.
  • Particular, polymerizable hydroxyl functional compounds include at least one diol, at least one triol, and/or at least one tetrol. Any of these polyol compounds may be monomelic, oligomeric, and/or polymeric as desired.
  • the polyol(s) may be selected from one or more hydroxyl functional polyethers, polyesters, polyurethanes, polyacrylics, epoxy resins, polyamides, polyamines, polyureas, polysulfones, castor oil, combinations of these, or the like.
  • Polyether polyols such as the polyalkylene ether and polyester polyols may be mentioned as these are commercially available at relatively low cost and are hydrolytically stable.
  • Suitable polyalkylene ether polyols include the poly(alkylene oxide) polymers such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and similar low molecular weight polyols.
  • Suitable commercially available polyether polyols include those sold under the trade name Voranol ® (The Dow Chemical Company).
  • the polyester polyols which are suitable in accordance with the invention include the known polycondensates of organic dihydroxy and optionally polyhydroxy (trihydroxy, tetrahydroxy) compounds and dicarboxylic and also optionally polycarboxylic (tricarboxylic, tetracarboxylic) acids or hydroxycarboxylic acids or lactones.
  • polycondensates of organic dihydroxy and optionally polyhydroxy (trihydroxy, tetrahydroxy) compounds and dicarboxylic and also optionally polycarboxylic (tricarboxylic, tetracarboxylic) acids or hydroxycarboxylic acids or lactones instead of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols to prepare the polyesters such as, for example, phthalic anhydride.
  • diols examples include ethylene glycol, 1 ,2-butanediol, diethylene glycol, triethylene glycol, polyalkylene glycols, such as polyethylene glycol, and also 1,2- and 1,3-propanediol, 1 ,4-butanediol, 1,6-hexanediol, neopentyl glycol or neopentyl glycol hydroxypivalate.
  • polyols having 3 or more hydroxyl groups in the molecule which may be used additionally, if desired, include trimethylolpropane, trimethylolethane, glycerol, erythritol, pentaerythritol, di- trimethylolpropane, dipentaerythritol, trimethylol-benzene or trishydroxyethyl isocyanurate.
  • a particularly suitable class of polyols useful in the compositions, foams and methods of the invention are the phthalic anhydride based polyester-ether polyols which are described, for example, in U.S. patent 6,855,844 which is incorporated by reference herein.
  • Suitable commercially available phthalic anhydride based polyester-ether polyols include the "Stepanpols" (Stepan Company).
  • suitable polyols are those having a viscosity at 25 degrees C of from about 500 to 15,000 cP and a hydroxyl number of from about 25 to 400.
  • the amount of polyisocyanate material employed in the invention should be sufficient to provide at least about 0.7 NCO group per reactive hydrogen present in the total reaction system.
  • substantially stochiometric amounts of NCO and OH groups are employed.
  • a stoichiometric excess of isocyanate compound (3 — 5%) is employed to obtain the flexible foams of the invention.
  • Stoichiometric excess generally means that the ratio of NCO groups of the polyisocyanate component to the OH groups of the polyol component is greater than 1 , specifically from greater than about 1.5 to about 20, more specifically from greater than about 2 to about 10, most specifically from greater than about 2.2 to about 10.
  • an NCO/OH molar ratio of about 2.5 to about 6 would be especially suitable to provide compositions that cure at a desirable rate to form foams with excellent pesticide retention characteristics.
  • levels may be specified within the scope of the invention.
  • cross-linking agents in the production of polyurethane foams is well known.
  • Polyfunctional alkanol amines are known to be useful for this purpose.
  • Suitable amines which may be included in the polyol formulation to aid or maintain the miscibility of the polyols include diethanolamine, often abbreviated as DEOA, triethanolamine, often abbreviated as TEOA, and glycerol.
  • 1,1-dichloro-l-fluoroethane R141b
  • chlorodifluoro-methane R22
  • 1-chloro- ljldifluoroethane R 142b
  • 1,1,1,2-tetrafluoro-ethane Rl 34a
  • aliphatic or cycloaliphatic C 3 -C 6 hydrocarbons such as propane, butane, n-pentane, isopentane, cyclopentane and cyclohexane.
  • water is used as the sole blowing agent to produce carbon dioxide by reaction with isocyanate.
  • water should be used at about 0.1 to about 10 parts per hundred parts of polyol, by weight (pphp), particularly between about 2 and about 8 pphp, more particularly between about 3 and about 6.5 pphp, most particularly between about 3.5 and about 5.8.
  • pphp parts per hundred parts of polyol, by weight
  • the stoichiometric excess of water blows via vaporization and cools the foam, and does not take part of the reaction to produce carbon dioxide.
  • suitable foams can generally be made using between about 0 and about 8 pphp, typically between about 0 and about 5 pphp, more typically between about 1 and about 3 pphp.
  • water is the key foaming agent. This can be introduced into the formulation directly as an added component or it can be added partially or wholly through the addition of the microencapsulated pesticide. Most microencapsulated products will be produced via an aqueous interfacial process, resulting in a dispersion of microcapsules in water. If the concentration of the capsules by such a process is suitable for use in these foam systems, the capsule product may be employed directly. If the amount of water resulting from the addition of such a capsule product is then also correct to produce an optimum foam, no further water need be added. If the water content from such a capsule product would be too high for an effective foam, the water content of the capsule product needs to be reduced.
  • the capsule product may be dried by any suitable technique (such as spray drying). Dry product may then be added directly to the foaming components (in either phase) and water and/or other foaming agents added independently.
  • suitable technique such as spray drying
  • Dry product may then be added directly to the foaming components (in either phase) and water and/or other foaming agents added independently.
  • Suitable spray-drying adjuvants include water-soluble salts such as ammonium sulfate or sodium, potassium or calcium chlorides.
  • the adjuvants may also include surfactants, water soluble polymers, higher alcohols and other water-soluble or water- dispersible components such as gums, clays and silica's.
  • chemistries are well known to those skilled in the art but include polymer stabilisers such as polyacrylic acids, polyvinyl alcohols (and their copolymers), polyvinylpyrrolidones (and their copolymers), surface active agents such as ethylene oxide-propylene oxide copolymers, naphthalene sulphonic acid- formaldehyde condensates and alkylbenzene sulphonates.
  • polymer stabilisers such as polyacrylic acids, polyvinyl alcohols (and their copolymers), polyvinylpyrrolidones (and their copolymers), surface active agents such as ethylene oxide-propylene oxide copolymers, naphthalene sulphonic acid- formaldehyde condensates and alkylbenzene sulphonates.
  • surface active agents such as ethylene oxide-propylene oxide copolymers
  • naphthalene sulphonic acid- formaldehyde condensates and alky
  • compositions of the invention may include an effective amount of a catalyst or reaction accelerator such as tertiary amines, metal-organic compounds, co- curatives, and the like.
  • a catalyst is, for example, from about 0.005 to 2 percent by weight of the reactive polyol and polyisocyanate components.
  • the catalyst is present at a level of about 0.01 to about 1.0 percent, based on the total weight of the polyisocyanate material and active hydrogen-containing material employed in the composition.
  • An exact amount can be readily determined by statistical analysis under the reaction conditions, including the actual polyol and polyisocyanate component reactivity, the anticipated reaction conditions, the equipment available, and the like, without undue experimentation.
  • Suitable catalysts useful in making polyurethane flexible foams are all those well known to the worker skilled in the art and include tertiary amines such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethylimidazole, N-methyl mo ⁇ holine, N-ethyl morpholine, triethylamine, tributylamine, triethanolamine, dimethylethanolamine and bis(dimethylaminoethyl) ether, organometallic tin compounds dibutyl tin dilaurate, dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate), dibutyltinbis(isooctyl maleate), , and other such tin salts.
  • tertiary amines such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethylimidazole,
  • Suitable blow catalysts can be used in their pure form or dissolved in a carrier such as a glycol, such as triethylenediamine in a dipropylene glycol carrier, which is commercially produced under the trade name Dabco ® LV-33 by the Air Products Corporation.
  • a carrier such as a glycol, such as triethylenediamine in a dipropylene glycol carrier, which is commercially produced under the trade name Dabco ® LV-33 by the Air Products Corporation.
  • the polyurethane foaming compositions will be formulated to produce a flexible foam that is optimized for the environment in which it is to be applied such as suitable open time to allow for uniform application and penetration, proper adhesion of the foam to the target substrate or locus, resistance of the foam to chemical degradation in basic or acidic environments, UV stability, etc., as the case may be.
  • suitable open time to allow for uniform application and penetration
  • proper adhesion of the foam to the target substrate or locus resistance of the foam to chemical degradation in basic or acidic environments, UV stability, etc., as the case may be.
  • flexible foams that are provided beneath concrete slabs are often exposed to a more alkaline environments than foams that are provided above a slab.
  • a sterically hindered polyol such as a phthalic anhydride based polyester polyol
  • a sterically hindered polyol such as a phthalic anhydride based polyester polyol
  • compositions of the invention may be employed with the foaming composition of the invention to impart to or modify particular characteristics of the composition.
  • the adjuvants should be added only at a level that does not materially adversely interfere with the stability of the microencapsulated pesticide or the adhesion of foams prepared from the composition.
  • the adjuvants may comprise up to 50 weight percent of the (polyol or polyisocyanate)/microencapsulated pesticide composition either individually or in combination.
  • chain-extension agents e.g., short chain polyols such as ethylene glycol or butanediol
  • fillers e.g., carbon black; glass, ceramic, metal or plastic bubbles; metal oxides such as zinc oxide; and minerals such as talc, clays, silica, silicates, and the like
  • thermoplastic resins plasticizers; antioxidants; pigments; U.V.
  • absorbers such as silicones and adhesion promoters such as silanes, and the like may be included to modify set time, open time, green strength build-up, tack, flexibility, adhesion, ductility, adhesive strength, gloss; elongation, pliability, buckling strength, crease resistance; as well as increased resistance to solvents, acids, bases, light, heat, cold, and sudden temperature changes, etc.
  • flame retardants can be incorporated to make the polyurethane foams of the present invention acceptable from a regulatory standpoint, for example, to be used in conjunction with building materials.
  • Useful flame retardants include, without limitation, any compound with flame suppression properties that can be dissolved or dispersed in the polyurethane foam. These include compounds such as chlorinated or brominated phosphates, phosphonates, inorganic oxides and chlorides.
  • the flame retardant is a soluble liquid such as triethyl phosphonate, pentabromodiphenyl oxide, and in particular is tri(l-methyl-2-chloroethyl) phosphate.
  • the flame retardants are employed in an amount of from 5 to 15 parts by weight.
  • composition mixture may be formulated such that the polyurethane foam may be made to cure to any useful color or shade as would be readily apparent to one skilled in the field of polyurethane foams.
  • colorants may be used to create foams with color.
  • the ratio of polyurethane to pesticidal product in the cured foam at the time that a foam of the composition is formed is at least 70:30 polymer: pesticide product, particularly 80:20 polyme ⁇ pesticide product and more particularly 85:15 polymer: pesticide product.
  • a filler such as fiber may be added to improve cohesion and flow characteristics of the foaming composition.
  • suitable fibers there may be mentioned glass fibers.
  • the fibers help to prevent the liquid surface uncured foam from sagging on pitched or vertical surfaces of target substrates during cure and to improve robustness and structural integrity of the cured foam.
  • Other solid fillers such as clay, calcium carbonate, and titanium dioxide are also contemplated.
  • polyols and polyisocyanates that can be used are those that are capable of forming a substantially water-impermeable polyurethane flexible foam upon curing.
  • the flexible foam is substantially water-impermeable, it is best tested by an appropriate water resistance test (for example, ASTM Method D 870-2).
  • ASTM Method D 870-2 ASTM Method D 870-2
  • the resultant polyurethane is one that is compatible with the polymer in the wall of the microcapsule employed in the composition.
  • polyurethane flexible foams having a thickness of from 0.1 to 10 mm are formed on a target substrate.
  • the foam thickness can be greater, indeed it can be employed to fill substantially completely the void space.
  • Those skilled in the art will adapt the foam thickness as appropriate under the prevailing circumstances.
  • the polyurethane flexible of the invention may be provided with a protective overcoat such as a latex or a polyurethane composition without a microencapsulated pesticide.
  • Latexes suitable as overcoats of the cured polyurethane foams are derived from a wide variety of polymers and co-polymers and combinations thereof.
  • Suitable latexes for use as overcoats comprise polymers and copolymers of styrene, alkyl styrenes, isoprene, butadiene, acrylonitrile lower alkyl acrylates, vinyl chloride, vinylidene chloride, vinyl esters of lower carboxylic acids and alpha, beta-ethylenically unsaturated carboxylic acids, including polymers containing three or more different monomer species copolymerized therein, as well as post-dispersed suspensions of silicones or polyurethanes.
  • the latex overcoats can be compounded with, or have mixed therein, other known ingredients such as plasticizers, emulsif ⁇ ers, stabilizers, curing agents, fillers, antioxidants, antiflexible foaming agents, dying adjuvants, levelling agents, pigments, or other compounding aids.
  • plasticizers emulsif ⁇ ers, stabilizers, curing agents, fillers, antioxidants, antiflexible foaming agents, dying adjuvants, levelling agents, pigments, or other compounding aids.
  • thickeners or bodying agents may be added to the polymer latexes so as to control the viscosity of the latexes and thereby achieve the proper flow properties for the particular application desired. Such materials are well known in the art.
  • the non-curable ingredients of the foaming composition and cured flexible foam herein further comprise at least one pesticide product comprising at least one microencapsulated pesticide and, optionally, one or more non-microencapsulated pesticides.
  • the microencapsulated pesticide portion of the pesticide product is present in an amount of at least 1% by weight of the cured foam.
  • the amount of any non-mi croencapsulated pesticides that are present in the composition are utilized in an amount of from 0 to about 99% by weight of the entire pesticide product present in the cured foam.
  • the pesticide products in the foaming composition and cured polyurethane foam including insecticides, acaricides and fungicides are employed in pesticidally effective amounts which will correspond to rates dependent on their activity levels for the desired end use.
  • suitable rates for the pesticide products are the existing rates given on the current product labels for such pesticide products.
  • Microencapsulated pesticide active ingredients suitable for use in the foaming compositions and cured flexible foams according to the invention are prepared with any suitable technique known in the art.
  • various processes for microencapsulating material have been previously developed. These processes can be divided into three categories-physical methods, phase separation and interfacial reaction.
  • microcapsule wall material and core particles are physically brought together and the wall material flows around the core particle to form the microcapsule.
  • phase separation category microcapsules are formed by emulsifying or dispersing the core material in an immiscible continuous phase in which the wall material is dissolved and caused to physically separate from the continuous phase, such as by coacervation, and deposit around the core particles.
  • microcapsules are formed by emulsifying or dispersing the core material in an immiscible continuous phase and then an interfacial polymerization reaction is caused to take place at the surface of the core particles.
  • concentration of the pesticidal active ingredient present in the microcapsules can vary from 0.1 to 60% by weight of the microcapsule.
  • Suitable microcapsules for use in the foamable compositions and polyurethane foams of the invention include microcapsules of both the relatively thin-walled quick-release type and the relatively thicker-walled controlled-release type or combinations thereof.
  • suitable microcapsule wall materials are selected from the polyureas, aminoplasts, polyurethanes and polyamides and mixtures thereof
  • polyurea microcapsules containing a suitable termiticide are prepared bas exemplified in U.S. Pat. No. 4,285,720, which involves the use of at least one polyisocyanate such as polymethylene polyphenylisocyanate (PMPPI) and/or tolylene diisocyanate (TDI) as the prepolymer.
  • PMPPI polymethylene polyphenylisocyanate
  • TDI tolylene diisocyanate
  • the wall- forming reaction is initiated by heating the emulsion to an elevated temperature at which point the isocyanate polymers are hydrolyzed at the interface to form amines, which in turn react with unhydrolyzed polymers to form the polyurea microcapsule wall.
  • Other suitable procedures for making microcapsules are described, for example, in Shirley et al., "Delivery of biological performance via micro-encapsulation formulation chemistry", Pest Management Science, Volume 57, Issue 2, Pages 129-132 (February 2001) and the references cited therein.
  • microencapsulated pesticides suitable for use in the invention will be produced via an aqueous interfacial process, resulting in a dispersion of microcapsules in water. If desired, the water may be decreased or removed from such systems.
  • Processes for production of relatively dry water-dispersible compositions of microencapsulated pesticides are described, for example, in U.S. Pat. Nos. 5,354,742 and 6,555,122 which are incorporated by reference herein.
  • the spray drying of the microcapsule is carried out under typical spray-drying conditions and with the use of typical spray-drying equipment in which the inlet temperatures generally range from about 105 to about 200 ° C. and output temperatures range from about 45 to about 95 ° C.
  • microcapsule suspension may also be advantageous to add to the microcapsule suspension prior to conducting the spray drying, typical spray drying adjuvants or additives such as clays, gums, surfactants, etc. as these may in general improve the spray drying procedure and the product quality obtained therefrom.
  • typical spray drying adjuvants or additives such as clays, gums, surfactants, etc. as these may in general improve the spray drying procedure and the product quality obtained therefrom.
  • suitable insecticidal, termiticidal or acaricidal active ingredients for use in the polyurethane foaming compositions and cured flexible foams include, but are not limited to, pyrethrins and synthetic pyrethroids; azoles, bisamides, oxadizine derivatives; chloronicotinyls; nitroguanidine derivatives; triazoles; organophosphates; pyrrols; pyrazoles; phenyl pyrazoles; diacylhydrazines; biological/fermentation products; carbamates and combinations of these types of compounds.
  • suitable insecticides, termiticides or acaricides for use in the inventive polyurethane foaming compositions and flexible foams include tefluthrin, permethrin, the cyhalothrins including lambda cyhalothrin and gamma cyhalothrin, resmethrin, deltamethrin, cypermethrin, cyphenothrin, cyfluthrin, deltamethrin, chlo ⁇ yrifos, fenoxycarb, diazinon, dichlorophen, methyl isothiocyanate, pentachlorophenol, tralomethrin, chlorfenapyr, fipronil, neonicotinoids and combinations of these compounds.
  • Suitable neonicotinoids include, but are not limited to, thiamethoxam, nitenpyram, imidacloprid, clothianidin, acetamiprid, and thiacloprid.
  • One specific class of pesticides for use in the microcapsules are the class of cyhalothrins including lambda cyhalothrin and gamma cyhalothrin.
  • suitable rates for the insecticide are the existing rates given on the current product labels for pesticide products containing such pesticide.
  • suitable fungicides for use in the polyurethane foaming composition and flexible foams include, but are not limited to, the azoles such as cyproconazole, propiconazole, tebuconazole and difenoconazole; the strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin; chlorothalonil; and thiabendazole.
  • suitable rates for the fungicide are the existing rates given on the current product labels for pesticide products containing such fungicide.
  • microencapsulated insecticides (optionally including at least one non-microencapsulated pesticide such as an insecticide or fungicide) are present in the foaming composition in an amount to provide an effective barrier to insect pests such as arthropods which contact or come into the vicinity of flexible foams prepared from the compositions.
  • insect pests such as arthropods which contact or come into the vicinity of flexible foams prepared from the compositions.
  • the exact amount will vary depending upon factors including the type of microcapsule employed, the substrate or locus to be treated as well as the thickness and orientation (horizontal or vertical) of the foam.
  • the insecticide of the foam must not prematurely dissipate and should be efficacious during that time in the target insects' life cycle which may cause potential damage to wood portions of a building or other construction.
  • the barrier foam of the present invention will contain an amount of insecticide that is insecticidally effective.
  • An insecticidally effective amount a used herein means that amount of insecticide that will kill insect pests or will consistently reduce or retard the amount of damage produced by insect pests.
  • target pests include insects and representatives of the order acarina such as termites, ants (such as carpenter ants) and spiders. More specifically, termites that may be controlled by the composition and method of the invention include, for example, Reticulitermes spp. such as R. ⁇ avipes, R. hesperus, R. tibialis, R. virginicus, K ' .santonensis and R. hageni and Coptotermes spp. such as C. formosanus.
  • Reticulitermes spp. such as R. ⁇ avipes, R. hesperus, R. tibialis, R. virginicus, K ' .santonensis and R. hageni and Coptotermes spp. such as C. formosanus.
  • the application methods such as spraying, misting, atomising, broadcasting, brushing, caulking, spreading, dipping or pouring, and the nature of the composition are adapted to suit the intended aims and the prevailing circumstances.
  • Optimum rates of application of the inventive composition, for a particular target substrate or locus and set of insect pressure conditions, can be determined easily and without undue experimentation by simple ranging studies carried out in wood such as in wooden building construction and wood which is in contact with soil for example fence posts, utility poles, railroad cross-ties and wooden supports, that can be structurally degraded by the action of one or more fungal or wood pests including, but not limited to, wood destructive fungi, termites, ants and other boring insects or arthropods.
  • the compositions of the invention are applied to substrates or loci such as clean, dry surfaces, typically concrete and cement including in and around concrete slab joints such as construction joints, key joints, tool joints and saw joints.
  • suitable targets include substrates such as plastic surfaces and substrates such as a DPM (Damp-proof membrane), vapor or moisture barriers or retarders and loci in or around structures, such as, homes, buildings, utility penetrations, bath traps, wall voids, wooden structures and other construction materials or construction substrates.
  • DPM Digital-proof membrane
  • vapor or moisture barriers or retarders in or around structures, such as, homes, buildings, utility penetrations, bath traps, wall voids, wooden structures and other construction materials or construction substrates.
  • DPM 's can be a simple polyethylene membrane, a chemically etched polyethylene (such as Corona treated polyethylene for greater wetting, substantivity of the polymer film to the polyethylene sheet) or re-enforced, structured multilayer polyethylene sheets such as the product range sold under the Tradename GRIFFOLYN® sold by Reef Industries, Inc. (Houston, TX).
  • the foaming compositions can also be applied to self-amalgamating tapes and films such as those composed of bitumous materials, butyl rubber, polyisobutene and the like, such as those sold under the Tradename Jiffy Seal® either prior to or after application of such self- amagamating materials to a target substrate such as a construction substrate, material or utility penetration such as a PVC or copper pipe or the like.
  • a target substrate such as a construction substrate, material or utility penetration such as a PVC or copper pipe or the like.
  • the foam is “cured”, or when “curing” the foam is referred to, what is meant is that a solid foam of components is formed from the polyol(s) and polyisocyanate(s) in the composition. Curing is often the result of a chemical reaction, adsorption, sequestration, or other forms of polymer curing that are known in the art.
  • the polyurethane foaming composition when applied onto substrates or in loci exhibits resistance to pests including termites such that if termites do attempt to feed or tunnel through the flexible foam, they find it not palatable or it causes mortality.
  • the main component used in the foaming composition that either causes mortality or makes it not palatable is a microencapsulated pesticide.
  • the cured physical polyurethane foam also contributes synergistically to this protection against insects such as arthropods including termites and wood-boring ants by inhibition of feeding.
  • Syngenta Crop Protection, Inc., Greensboro, NC is added to 218g of a surfactant solution prepared from 30Og of water, 6.Og of Morwet ® D425 (sodium sulfonate of naphthalene formaldehyde condensate/ Witco) and 0.7g of HiSiI 233 (silica filler/ PPG).
  • the components are thoroughly mixed until a stable mixture is formed.
  • Sprayed-dried Demand CS is obtained by pumping the mixture at 21-22 ml/min into a spray drier having an inlet temperature of 105° C and an outlet temperature of 74-75° C.
  • T- 12 (Dibutyltin dilaurate) 0.02
  • Voranol 230-112 (EOPO polyether polyol) 25
  • Voranol 230-112 (EOPO polyether polyol) 20
  • TC-276A is an aromatic diisocyante and related oligomers based on 4,4 - phenylmethane diisocyanate (MDI).
  • TC-276B is a polyol resin based on propylene oxide, ethylene oxide based polyglycols.
  • This slurry was spray dried with an inlet tempearture of 170 0 C and an outlet temperature of 66°C to yield a solid product containing 22.5% Lambda-cyhalothrin.
  • the Lambda-cyhalothrin granules were dispersed in the PPG425. This was the first feedstock stream.
  • the Stepanpol, diethanolamine, Dabco 33LV and Dibutyltin dilaurate were blended together as the second feedstock stream and then the appropriate net weight of this mixture was added to the first feedstock stream (PPG425 / lambda-cyhalothrin base).
  • the third feestock stream (Rubinate M) was addedand vigorously stirred in for 20 seconds.
  • the mixture was divided into 4 smaller portions, each one of which rose and set to form a non-tacky, flexible foam.
  • a sample of about 1 gram of each foam prepared and in accordance with examples 2 - 8 each containing a given % by weight of microencapsulated pesticide is transferred to a 2 oz bottle. 20 ml of tetrahydrofuran (THF) solvent is added to the bottle and sonicated in a water bath for about 30 minutes. Each sample is filtered through a 0.45 micron filter and analyzed for lambda cyhalothrin by HPLC. The percentage of lambda cyhalothrin remaining in the each sample one month after treatment is calculated. The results are reported in the table below.
  • THF tetrahydrofuran
  • this invention provides a new curable polyurethane composition containing a microencapsulated pesticide, flexible foam barriers prepared therefrom, and methods of making the same. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.

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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)

Abstract

La présente invention se rapporte à une composition moussante à base de polyuréthanne durcissable contenant un pesticide micro-encapsulé, à des mousses souples préparées à partir de ladite composition, et à des procédés de fabrication associés.
PCT/US2006/029987 2005-08-04 2006-08-01 Compositions moussantes a base d'urethanne destinees a la lutte contre les ravageurs WO2007019148A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016153578A1 (fr) * 2015-03-20 2016-09-29 Pero Michael A Iii Système pour la fabrication de feuilles en mousse rigidifiées par infiltration polymère
CN106632974A (zh) * 2016-09-22 2017-05-10 上海馨源新材料科技有限公司 一种酯醚型汽车用顶棚用海绵及制作工艺
WO2019204625A1 (fr) * 2018-04-18 2019-10-24 Frx Polymers, Inc. Compositions ignifuges sans halogène pour mousses de polyuréthane souples

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061740A (en) * 1975-11-18 1977-12-06 American Cyanamid Company Liquid compositions containing a polyethylene glycol safener and an organophosphorus pesticide
US5098621A (en) * 1985-01-07 1992-03-24 Twin Rivers Engineering Method of forming a foam substrate and micropackaged active ingredient particle composite
US5698210A (en) * 1995-03-17 1997-12-16 Lee County Mosquito Control District Controlled delivery compositions and processes for treating organisms in a column of water or on land
US6036970A (en) * 1994-12-13 2000-03-14 Bayer Aktiengesellschaft Rodenticidal foams

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061740A (en) * 1975-11-18 1977-12-06 American Cyanamid Company Liquid compositions containing a polyethylene glycol safener and an organophosphorus pesticide
US5098621A (en) * 1985-01-07 1992-03-24 Twin Rivers Engineering Method of forming a foam substrate and micropackaged active ingredient particle composite
US6036970A (en) * 1994-12-13 2000-03-14 Bayer Aktiengesellschaft Rodenticidal foams
US5698210A (en) * 1995-03-17 1997-12-16 Lee County Mosquito Control District Controlled delivery compositions and processes for treating organisms in a column of water or on land

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016153578A1 (fr) * 2015-03-20 2016-09-29 Pero Michael A Iii Système pour la fabrication de feuilles en mousse rigidifiées par infiltration polymère
US9694897B2 (en) 2015-03-20 2017-07-04 Michael A. Pero, Iii System for manufacture of foam sheets rigidized with polymer infiltration
US10053206B2 (en) 2015-03-20 2018-08-21 Michael A. Pero, Iii System for manufacture of foam sheet rigidized with polymer infiltration
CN106632974A (zh) * 2016-09-22 2017-05-10 上海馨源新材料科技有限公司 一种酯醚型汽车用顶棚用海绵及制作工艺
WO2019204625A1 (fr) * 2018-04-18 2019-10-24 Frx Polymers, Inc. Compositions ignifuges sans halogène pour mousses de polyuréthane souples

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