Pest control composition

Abstract

A pest control composition comprising a plurality of composite particles, each of the composite particles comprising a polyolefin core wherein a polyolefin of the polyolefin core has a monomer structural unit derived from an olefin monomer in an amount of 50 wt% or more based on the total weight of the polyolefin. Each of the composite particles further includes a plurality of monomer structural units derived from a vinyl monomer polymerized onto the polyolefin core, wherein the vinyl monomer includes one or more (meth) acrylic monomers. The composition further comprises bacillus thuringiensis and water.

Description

Technical Field

[0001] The present disclosure relates generally to pest control compositions, and more particularly to pest control compositions including composite particles. Background Art

[0002] Pest control agents are used to control pests, such as insects. The effectiveness of a pest control agent can be affected by many factors. Industry continues to focus on developing new and improved pest control compositions. Summary of the invention

[0003] According to the first feature of the present disclosure, a pest control composition includes a plurality of composite particles, each of which includes a polyolefin core, wherein the polyolefin of the polyolefin core has a monomer structural unit derived from an olefin monomer of 50% by weight or more based on the total weight of the polyolefin. Each composite particle in the composite particle also includes a plurality of monomer structural units derived from a vinyl monomer polymerized onto the polyolefin core, wherein the vinyl monomer includes one or more (meth) acrylic monomers. The composition also includes bacillus thuringiensis and water. According to the second feature of the present disclosure, based on the total weight of the combination of composite particles, pest control agents and water, the composite particles are 0.1% by weight to 15.0% by weight of the composition. According to the third feature of the present disclosure, the polyolefin core of the composite particles includes ethylene / octene copolymers. According to the fourth feature of the present disclosure, based on the total weight of the combination of composite particles, pest control agents and water, water is 20.00% by weight to 99.89% by weight of the composition. According to the fifth feature of the present disclosure, the composite particles have a weight ratio of a polyolefin core to a monomer structural unit derived from a vinyl monomer of 90:10 to 60:40. According to the sixth feature, the composite particles have a weight ratio of the polyolefin core to the monomer structural units derived from the vinyl monomer of 80:20. According to the seventh feature, the polyolefin core is crosslinked. DETAILED DESCRIPTION

[0004] Unless otherwise indicated, all ranges are inclusive. Subscript values ​​in polymer formulas refer to the molar average of the designated components of the polymer.

[0005] Test methods refer to the most recent test methods as of the priority date of this document, unless the date is expressed as a two-digit number with a hyphen in the test method number. Reference to a test method includes reference to both the testing association and the test method number. Test method organizations are referenced by one of the following abbreviations: ASTM refers to ASTM International (formerly the American Society for Testing and Materials); EN refers to European Standards; DIN refers to the German Institute for Standardization; and ISO refers to the International Organization for Standardization.

[0006] As used herein, unless specifically stated to the contrary, "wt %" or "weight percent" or "weight %" of a component is based on the total weight of the composition or article including the component. Unless otherwise indicated, all percentages are by weight.

[0007] Disclosed herein are pest control compositions. Embodiments of the present disclosure provide pest control compositions comprising a plurality of composite particles, Bacillus thuringiensis, and water.

[0008] The pest control compositions disclosed herein can be applied to plants (e.g., plant surfaces) to control pests. Advantageously, the pest control compositions disclosed herein can provide improved (i.e., greater) residual protein concentrations for Bacillus thuringiensis after exposure to rainwater compared to other formulations. The improved residual protein concentrations indicate that the pest control compositions disclosed herein can provide improved pest control compared to other formulations.

[0009] In addition, the pest control compositions disclosed herein can provide a percentage of Bacillus thuringiensis activity that remains greater than 80% after exposure to rain. Providing a percentage of Bacillus thuringiensis activity that remains greater than 80% can indicate a desired degree of resistance to rain washout.

[0010] The pest control composition disclosed herein includes a plurality of composite particles. Embodiments of the present disclosure provide that each composite particle in the composite particles includes a polyolefin core and a plurality of monomer structural units derived from vinyl monomers polymerized onto the polyolefin core. The term "shell" may be used herein to generally describe the polymerization of a plurality of monomer structural units derived from vinyl monomers onto the polyolefin core, but the term "shell" in no way limits the distribution, orientation, spacing or continuity of the monomer structural units derived from vinyl monomers across the core.

[0011] As mentioned, the composite particles include a polyolefin core, such as a core polymer. As used herein, a "polymer" has two or more identical or different monomer structural units, which are derived from a variety of monomers, such as homopolymers, copolymers, terpolymers, etc. "Monomer structural units" used herein with respect to polymers indicate a portion of a polymer structure produced by a reaction of one or more monomers to form a polymer. "Different" with respect to monomer structural units indicates that the monomer polymer structural units differ from each other by at least one atom or isomer. As used herein, "polyolefin" refers to a polymer having 50% by weight or more of monomer structural units derived from olefins based on the total weight of the polymer. "Olefin" refers to a compound, such as a monomer, that is a hydrocarbon having one or more carbon-carbon double bonds and not having an aromatic ring. As used herein, "one" refers to one or more, unless otherwise specified. The polyolefin core can be cross-linked.

[0012] The core polymer includes a polyolefin. Embodiments of the present disclosure provide that the core polymer may include a hydrocarbon polyolefin and / or a non-hydrocarbon polyolefin. A polyolefin that includes monomer structural units derived only from hydrocarbon monomers is considered a hydrocarbon polyolefin, even if there are small amounts of hetero groups, such as fragments that serve as initiators and / or chain transfer agents, attached to the polyolefin. For hydrocarbon polyolefins, the molar ratio of heteroatoms to polymerized units of all monomers is 0.001:1 or less. Polyolefins that are not hydrocarbon polyolefins are considered non-hydrocarbon polyolefins, such as polyolefins that include one or more hetero groups. As used herein, atoms other than carbon and hydrogen are considered "hetero" atoms; chemical groups containing one or more heteroatoms are considered "hetero" groups.

[0013] Examples of hydrocarbon polyolefins include, but are not limited to, hydrocarbon polyolefins having monomer structural units derived from ethylene and one or more α-olefins. Examples of α-olefins include propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and combinations thereof. Other examples of hydrocarbon polyolefins include polymers of one or more dienes with ethylene, with one or more α-olefins, or with combinations thereof. Examples of dienes include butadiene; dicyclopentadiene; 1,5-hexadiene; ethylidene norbornene; and vinyl norbornene.

[0014] The hydrocarbon polyolefins can be prepared using known equipment, reaction components and reaction conditions. The hydrocarbon polyolefins can be obtained commercially. Examples of suitable commercially available hydrocarbon polyolefins include, but are not limited to, those sold under the trade name VERSIFY TM 、NORDEL TM or ENGAGE TM Those available from The Dow Chemical Company, and under the trade name VISTAMAXX TM 、VISTALON TM or EXACT TM Those available from ExxonMobil Chemical Company.

[0015] As mentioned above, the core polymer may include a non-hydrocarbon polyolefin. The non-hydrocarbon polyolefin may include hetero groups. Examples of hetero groups include, but are not limited to, carboxyl groups, ester groups, anhydride groups, alkoxysilane groups, and combinations thereof. The hetero groups may be attached to the comonomer before polymerization, or may be added to the non-hydrocarbon polyolefin by grafting after polymerization. One or more embodiments of the present disclosure may use maleic anhydride grafted onto the hydrocarbon polyolefin. Unsaturated compounds containing heteroatoms may be grafted onto the hydrocarbon polyolefin by any effective method, such as by free radical methods, such as in the presence of a free radical initiator or in the presence of ionizing radiation. Examples of non-hydrocarbon polyolefins are copolymers of one or more alpha-olefins with one or more monomers such as vinyl acetate, ethyl acrylate, vinyl alcohol, vinyl chloride, and (meth) acrylic monomers.

[0016] The non-hydrocarbon polyolefins can be prepared using known equipment, reaction components and reaction conditions. The non-hydrocarbon polyolefins can be obtained commercially. Examples of suitable commercially available non-hydrocarbon polyolefins include, but are not limited to, those sold under the trade name AMPLIFY TM 、PARALOID TM or RETAIN TM Those available from The Dow Chemical Company under the trade name FUSABOND TM Those available from EI DuPont de Nemours under the trade name POLYBOND TM Those available from Chemtura Corporation, and under the trade name LICOCENE TM The polymers were those available from Clariant International Ltd.

[0017] The polyolefin core may include a crosslinking agent. For example, the crosslinking agent may be used to crosslink the polyolefin of the polyolefin core. The crosslinking agent may be a monomeric crosslinking agent, a polymeric crosslinking agent, or a combination thereof. Examples of crosslinking agents include, but are not limited to, triallyl isocyanurate; 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; triallyl cyanurate; triallyl trimellitate; tri(methylallyl) isocyanurate; tri(diallylamine)-s-triazine; triallyl phosphite; N,N-diallylacrylamide, N,N,N',N',N",N"-hexaallylphosphoramide; N,N,N',N'-tetraallylterephthalamide; N,N,N',N'-tetraallylinalonamide; trivinyl isocyanurate; methyl-2,4,6-trivinyltrisiloxane; N,N'-m-phenylenebismaleimide; diallyl phthalate; tris(5-norbornyl-2-methylene)cyanurate; and combinations thereof. The monomeric crosslinking agent may have two or more carbon-carbon double bonds; or 3 or more carbon-carbon double bonds. Examples of polymeric crosslinking agents include, but are not limited to, polyolefins having carbon-carbon double bonds. The polymeric crosslinking agent may be a homopolymer, a copolymer, or a combination thereof containing monomeric structural units derived from one or more dienes.

[0018] The polyolefin core can be prepared using known equipment, reaction components and reaction conditions. One example of a suitable method for preparing the polyolefin core is as follows.

[0019] One or more hydrocarbon polyolefins and one or more non-hydrocarbon polyolefins can be fed into the extruder via a feed throat. The hydrocarbon polyolefin and the non-hydrocarbon polyolefin can be added to the extruder separately; can be mixed together and then added to the extruder as a mixture; or can be compounded together by melt mixing before being added to the extruder. If the crosslinking agent is solid at 25°C, it can also be fed through the feed throat together with the hydrocarbon polyolefin and the non-hydrocarbon polyolefin. If the crosslinking agent is liquid at 25°C, it can be injected into the melting zone of the extruder via a pump. The hydrocarbon polyolefin, the non-hydrocarbon polyolefin and the crosslinking agent can be mixed together in a molten state in the extruder and then emulsified in the extruder by adding water and a surfactant via a pump. Water can be added to provide the desired solid content. For example, the emulsion can have a water content of 60% to 90% by weight based on the total weight of the emulsion. Such an emulsion can have a solid content of 5% to 50% by weight based on the total weight of the emulsion. The surfactant can be an emulsion of 0.5% to 10% by weight based on the total weight of the solids of the emulsion. As used herein, the terms "emulsion" and "dispersion" are used interchangeably. Examples of commercially available surfactants include those sold under the trade name EMPICOL TM Those purchased.

[0020] The surfactant may be an anionic surfactant comprising a hydrocarbon group of 8 or more carbon atoms and an anionic group. The hydrocarbon group may be linear, branched, aromatic, or a combination thereof. Anionic groups are chemical groups that carry a negative charge in water at a pH of 7. Examples of anionic groups include, but are not limited to, phosphate groups, phosphonate groups, carboxylate groups, sulfate groups, and sulfonate groups. Anionic surfactants may include (CH2CH2O) n A group wherein n is 1 to 20. For example, (CH2CH2O) n The group may be bonded to a sulfate group.

[0021] A method of making such an emulsion is described in U.S. Publication No. 2016 / 0177077. Additional water may then be added to the extruder to provide a dispersion exiting the extruder having a solids content of less than 70 wt % based on the total weight of the dispersion. One or more embodiments provide for first emulsifying the polyolefin as described above and then adding the crosslinking agent to the emulsion, preferably while the emulsion is maintained at a temperature above the melting point of the one or more polyolefins.

[0022] After the dispersion prepared from the hydrocarbon polyolefin, the non-hydrocarbon and the crosslinking agent is formed, an initiator such as a peroxide initiator can be combined with the dispersion. The peroxide initiator can have the structure R 1 -OOR 2 , where R 1 and R 2 Each is independently H or an organic group. 1 and R 2 Each of the peroxide initiators may be independently H or an alkyl group, for example, an alkyl group independently having 2 to 12 carbon atoms. Examples of peroxide initiators include, but are not limited to, hydrogen peroxide, alkyl hydroperoxides, tert-butyl hydroperoxides, and combinations thereof. The peroxide initiator may be

[0023] It is used at a concentration of 0.02 wt % to 2 wt % based on the total weight of solids of the emulsion.Examples of other suitable initiators include thermal initiators and photoinitiators.

[0024] When the initiator is combined with the dispersion, a reducing agent may be used, for example to form a redox initiator with the peroxide initiator. Examples of reducing agents include, but are not limited to, ascorbic acid, isoascorbic acid, sodium formaldehyde sulfoxylate, tetramethylethylenediamine, sodium metabisulfite, and combinations thereof. The molar ratio of the peroxide to the reducing agent may be 0.7:1 or higher; 0.8:1 or higher; or 0.9:1 or higher; the molar ratio of the peroxide to the reducing agent may be 1.3:1 or lower; 1.2:1 or lower; or 1.1:1 or lower. An oxidation / reduction catalyst may be used for the oxidation / reduction reaction between the peroxide initiator and the reducing agent. Examples of oxidation / reduction catalysts include, but are not limited to, salts of iron (II); FeSO4 may be used. The oxidation / reduction catalyst may be used at a concentration of 1 part per million (ppm) to 50 ppm based on the total weight of the solids of the emulsion.

[0025] The polyolefin core can include 50 wt % to 95 wt % hydrocarbon polyolefin based on the total weight of the polyolefin core, for example, based on the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin and the crosslinking agent, so that the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin and the crosslinking agent sums to 100 wt %. All individual values ​​and subranges from 50 wt % to 95 wt % are included; for example, the polyolefin core can have a lower limit of 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt % or 75 wt % to an upper limit of 95 wt %, 92 wt %, 90 wt %, 85 wt %, 83 wt % or 80 wt % hydrocarbon polyolefin based on the total weight of the polyolefin core.

[0026] The polyolefin core may include 2 wt % to 50 wt % of non-hydrocarbon polyolefin, based on the total weight of the polyolefin core, e.g., based on the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin, and the crosslinking agent, such that the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin, and the crosslinking agent sums to 100 wt %. All individual values ​​and subranges from 2 wt % to 50 wt % are included; for example, the polyolefin core may have a lower limit of 2 wt %, 3 wt %, 5 wt %, 7.5 wt %, 10 wt %, or 12 wt % to an upper limit of 50 wt %, 45 wt %, 40 wt %, 35 wt %, 30 wt %, or 20 wt % of non-hydrocarbon polyolefin, based on the total weight of the polyolefin core.

[0027] The polyolefin core may include 0.5 wt % to 20 wt % crosslinking agent based on the total weight of the polyolefin core, e.g., based on the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin, and the crosslinking agent, such that the total weight of the hydrocarbon polyolefin, the non-hydrocarbon polyolefin, and the crosslinking agent sums to 100 wt %. All individual values ​​and subranges from 0.5 wt % to 20 wt % are included; for example, the polyolefin core may have a lower limit of 0.5 wt %, 1.0 wt %, 1.5 wt %, 2.0 wt %, 2.5 wt %, or 3.0 wt % to an upper limit of 20 wt %, 18 wt %, 15 wt %, 12 wt %, or 10 wt % crosslinking agent based on the total weight of the polyolefin core.

[0028] As mentioned, the composite particles comprise a polyolefin core and a shell, the shell comprising monomer structural units derived from vinyl monomers. The composite particles may be prepared by emulsion polymerization to form the shell; for example, using one or more vinyl monomers in the presence of a polyolefin core particle.

[0029] For example, one or more vinyl monomers can be combined with water and surfactant to form an emulsion of drops in an aqueous medium, wherein the drops contain vinyl monomers, such as (meth) acrylic monomers. Then, a dispersion (such as, as previously discussed, an emulsion of vinyl monomer drops) and a mixture of water-soluble initiators comprising polyolefin core particles can be formed. The mixture can be subjected to known emulsion polymerization conditions, which cause the initiator to produce free radicals and shells, such as polymers comprising monomer structural units derived from vinyl monomers.

[0030] Examples of vinyl monomers include (meth) acrylic monomers, vinyl aromatic monomers and combinations thereof. Examples of (meth) acrylic monomers include, but are not limited to, (meth) acrylic acid, its unsubstituted alkyl esters, its substituted alkyl esters and combinations thereof. Examples of unsubstituted alkyl acrylates include, but are not limited to, those in which the alkyl group has 2 to 18 carbon atoms. Examples of unsubstituted alkyl methacrylates include, but are not limited to, those in which the alkyl group has 1 to 4 carbon atoms. One or more embodiments provide that the vinyl monomer is methyl methacrylate, butyl acrylate or a combination thereof.

[0031] Embodiments of the present disclosure provide that the composite particles have a weight ratio of the polyolefin core particles to the plurality of monomer structural units derived from the vinyl monomer of 90:10 to 60:40. All individual values ​​and subranges of 90:10 to 60:40 are included; for example, the composite particles may have a weight ratio of the polyolefin core particles to the plurality of monomer structural units derived from the vinyl monomer of 90:10; 85:15; 80:20; 75:25; 70:30; 65:35; or 60:40.

[0032] After the emulsion polymerization process for forming composite particles and / or dilutions, the composite particles can be dispersed in an aqueous medium. Various amounts of water can be used for different applications. For example, the dispersion comprising composite particles can be a solid of 15 wt % to 85 wt % based on the gross weight (e.g., the gross weight of solid components and liquid components) of the dispersion. All individual values ​​and subranges of 15 wt % to 85 wt % are included; for example, the dispersion comprising composite particles can have a lower limit of 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt % or 40 wt % to an upper limit of 85 wt %, 80 wt %, 75 wt %, 70 wt %, 65 wt % or 60 wt % based on the gross weight of the dispersion.

[0033] The composite particles can have a volume average particle size of 100 nanometers (nm) to 2000 nm. All individual values ​​and subranges of 100 nm to 2000 nm are included; for example, the composite particles can have a volume average particle size of 100 nm, 150 nm, 200 nm, or 250 nm at a lower limit to 2000 nm, 1000 nm, 750 nm, or 500 nm at an upper limit. Particle size analysis was performed using a Beckman Coulter LS13320 laser scattering particle size analyzer (Beckman Coulter Inc., Fullerton, CA).

[0034] The pest control composition disclosed herein includes the plurality of composite particles, wherein the composite particles include a polyolefin core and a shell, the shell including monomer structural units derived from a vinyl monomer, as discussed herein. The composite particles can be used as a component of a dispersion in a pest control composition. The composite particles can be used as a powder in a pest control composition; for example, a dispersion containing the composite particles can be dried to provide a powder containing the composite particles. Suitable methods for removing water (i.e., drying) from a dispersion including the composite particles include, for example, spray drying and coagulation.

[0035] The pest control composition disclosed herein includes Bacillus thuringiensis. As defined herein, "Bacillus thuringiensis" is the spores and / or crystalline proteins of the Bacillus thuringiensis species, and includes all Bacillus thuringiensis subspecies that exhibit insecticidal properties. Examples of such subspecies include Kurstaki, Israelensis, and Aizawa. Bacillus thuringiensis can be added to the insecticide formulation as a solid or as part of a liquid formulation. The presence and subspecies of Bacillus thuringiensis are determined by random amplification polymorphic DNA analysis. Commercially available liquid formulations of Bacillus thuringiensis are THURICIDE manufactured by CERTIS USA of Columbia, Maryland. TMInsecticides. Bacillus thuringiensis can produce insecticidal crystal proteins, such as Cry proteins and Cyt proteins, by spore formation. After exposure to light, greater activity can provide advantageously improved pest control. After exposure to rain, greater residual protein concentrations (e.g., residual Cry protein concentrations and / or Cyt protein concentrations) can provide advantageously improved pest control.

[0036] The pest control compositions disclosed herein may include water. Different amounts of water may be used for different applications.

[0037] One or more embodiments of the present disclosure provide that the pest control composition disclosed herein may include additives. Examples of additives include viscosity modifiers, pH modifiers, herbicides, fungicides, and combinations thereof, etc. Different amounts of additives can be used for various applications.

[0038] As mentioned, the pest control compositions disclosed herein include composite particles. Based on the total weight of the combination of the composite particles, Bacillus thuringiensis, and water, the composite particles can be 0.1% to 15.0% by weight of the pest control composition. For example, the composite particles can be 0.1% or more, or 0.5% or more, or 1.0% or more, or 1.5% or more, or 2.0% or more, or 2.5% or more, or 3.0% or more, or 3.5% or more, or 4.0% or more, or 4.5% or more, or 5.0% or more, or 5.5% or more, or 6.0% or more, or 6.5% or more, of the combination of the composite particles, Bacillus thuringiensis, and water. % or more, or 7.0 wt % or more, or 7.5 wt % or more, or 8.0 wt % or more, or 8.5 wt % or more, or 9.0 wt % or more, or 9.5 wt % or more, or 10.0 wt % or more, or 10.5 wt % or more, or 11.0 wt % or more, or 11.5 wt % or more, or 12.0 wt % or more, or 12.5 wt % or more, or 13.0 wt % or more, or 13.5 wt % or more, or 14.0 wt % or more, or 14.5 wt % or more, while 15.0 wt % or less, or 14.5 wt % or less, or 14.0 wt % or less, or 13.5 wt % or less, or 13.0 wt % or less, or 12.5 wt % or less, or 12.0 wt % or less, or 11.5 wt % or less, or 11.0 wt % or less, or 10.5 wt % or less, or 10.0 wt % or less, or 9.5 wt % or less, or 9.0 wt % or less, or 8.5 wt % or less , or 8.0 wt % or less, or 7.5 wt % or less, or 7.0 wt % or less, or 6.5 wt % or less, or 6.0 wt % or less, or 5.5 wt % or less, or 5.0 wt % or less, or 4.5 wt % or less, or 4.0 wt % or less, or 3.5 wt % or less, or 3.0 wt % or less, or 2.5 wt % or less, or 2.0 wt % or less, or 1.5 wt % or less, or 1.0 wt % or less, or 0.5 wt % or less.

[0039] The pest control composition disclosed herein includes Bacillus thuringiensis. Based on the total weight of the combination of composite particles, Bacillus thuringiensis and water, Bacillus thuringiensis can be 0.01% to 25.00% by weight of the pest control composition. All individual values ​​and subranges from 0.01% to 25.00% by weight are included; for example, based on the total weight of the combination of composite particles, Bacillus thuringiensis and water, the pest control composition can include a lower limit of 0.01%, 0.05% or 1.0% by weight to an upper limit of 25.00%, 15.00% or 10.00% by weight of Bacillus thuringiensis.

[0040] The pest control composition disclosed herein includes water. Based on the total weight of the combination of composite particles, Bacillus thuringiensis and water, water can be 60.00% to 99.89% by weight of the pest control composition. All individual values ​​and subranges from 20.00% to 99.89% by weight are included; for example, based on the total weight of the combination of composite particles, Bacillus thuringiensis and water, the pest control composition can include a lower limit of 20.00%, 30.00% or 40.00% by weight to an upper limit of 99.89%, 98.00% or 95.00% by weight of water. Water can be incorporated into the pest control composition via a dispersion containing composite particles and / or water can be incorporated into the pest control composition by addition independent of the dispersion.

[0041] The pest control composition disclosed herein can be formed using known equipment and methods. The components of the pest control composition can be combined (e.g., mixed) to form the pest control composition. For example, the components of the pest control composition can be added to a container and stirred therein. The components of the pest control composition can be combined in any order.

[0042] The pest control composition disclosed herein can be applied to plants (e.g., plant surfaces) to control pests. The pest control composition can be applied to plants using known equipment and methods. For example, among other applications, the pest control composition can be sprayed, sprinkled, and / or poured onto plants. Different amounts of the pest control composition can be applied to plants for various applications.

[0043] Example

[0044] In the Examples, various terms and names of materials are used, including, for example, the following:

[0045] ENGAGE TM 8137 (hydrocarbon polyolefin, ethylene-octene copolymer, available from The Dow Chemical Company); LICOCENE TMPR MA 4351 (non-hydrocarbon polyolefin, maleated polyethylene wax, 5 weight percent maleic anhydride, available from Clariant); RETAIN TM 3000 (non-hydrocarbon polyolefin, ethylene / octene copolymer grafted with maleic anhydride groups, available from The Dow Chemical Company); EMPICOL TM ESB 70 (surfactant, sodium lauryl ether sulfate, available from Huntsman); triallyl isocyanurate (crosslinker, available from Nippon Kasei Chemicals); methyl methacrylate (vinyl monomer); butyl acrylate (vinyl monomer); polyethylene-polyvinyl acetate copolymer (20 wt% polyethylene, 80 wt% vinyl acetate, CAS No: 24937-78-8, available from Polysciences Inc).

[0046] Composite particles were formed as follows. An aqueous polyolefin dispersion (referred to as the first dispersion) including polyolefin core particles was prepared using a twin-screw extruder (25 mm screw diameter, 48 L / D, rotating at 450 rpm). TM 8137、LICOCENE TM PE MA 4351 and RETAIN TM 3000 was supplied to the feed throat of the extruder via a Schenck Mechatron loss-in-weight feeder and a Schenck volumetric feeder, respectively. Triallyl isocyanurate was injected into the polymer melt zone using an Isco dual syringe pump (available from Teledyne Isco, Inc.). The polymers were melt blended and then heated in a first water stream and EMPICOL TM The emulsion phase is then conveyed forward to the dilution and cooling zone of the extruder where additional water is added to form an aqueous dispersion having a solids content of less than 70% by weight, i.e., the first dispersion. The first water stream and the dilution water are supplied by an Isco dual syringe pump. The barrel temperature of the extruder is set at 140°C to 150°C. After the dispersion leaves the extruder, it is further cooled and filtered through a bag filter with a mesh size of 200 μm. The aqueous polyolefin dispersion is 50% by weight solids in water and includes polyolefin core particles, the aqueous polyolefin dispersion comprising: ENGAGE TM 8137 (79% by weight); LICOCENE TM 4351(5 wt%); RETAIN TM 3000 (10 wt%); EMPICOL TM ESB (4 wt%); triallyl isocyanurate (2 wt%).

[0047] In a 1L three-necked flask equipped with a condenser and a mechanical stirrer, the first dispersion (i.e., a polyolefin dispersion including polyolefin core particles) was diluted with water to about 40% solids by weight at a pH of 4 to 5. The stirring rod was inserted through a Teflon adapter and a glass sleeve and assembled through the center neck of the flask. The stirrer rate was set to 200 rpm and nitrogen was slowly purged through the reactor; the cooling water was turned on to flow through the condenser. Next, 5 ppm of iron (II) sulfate heptahydrate and 25 ppm of ethylenediaminetetraacetic acid (EDTA) based on the total weight of the diluted dispersion were added, and the mixture was heated to 65°C using a heating jacket. A solution of tert-butyl hydroperoxide (t-BHP, 0.3% by weight based on the total weight of the diluted dispersion) and sodium formaldehyde sulfoxylate (SFS, 0.3% by weight based on the total weight of the diluted dispersion) in deionized water was fed into the reactor using a syringe pump within 60 minutes. The reactor was then kept at 65°C for 30 minutes. Separately, a monomer emulsion comprising methyl methacrylate (98 wt %) and butyl acrylate (2 wt %) was prepared in deionized water in the presence of sodium dodecylbenzene sulfonate (DS-4, 0.04 wt % based on the total weight of methyl methacrylate and butyl acrylate). A solution of t-BHP (0.2 wt % based on the total weight of methyl methacrylate and butyl acrylate) and SFS (0.17 wt % based on the total weight of methyl methacrylate and butyl acrylate) in deionized water was prepared and loaded into a syringe pump for delivery. The monomer emulsion and t-BHP / SFS solution were co-fed into the reactor simultaneously at 65°C. The monomer emulsion was fed over 60 minutes, and the t-BHP / SFS solution was fed over a total of 90 minutes. The reactor was then held at 65°C for 30 minutes, and the reactor contents, i.e., a dispersion comprising composite particles as discussed herein (which is referred to as the second dispersion), were then cooled to about 25°C to filter through a 150 μm mesh filter. For the composite particles, the weight ratio of the polyolefin core particles to the plurality of monomer structural units derived from the vinyl monomer was 80:20. The dispersion was 42.0 wt% solid and the composite particles had a volume average particle size of 350 nanometers. Particle size analysis was performed using a Beckman Coulter LS 13320 laser scattering particle size analyzer (Beckman Coulter Inc., Fullerton, California).

[0048] Example 1, a pest control composition, was formed as follows. A portion of the second dispersion, THURICIDE TM and water to provide Example 1. Example 1 included 2.5 wt% of the composite particles, and the resulting formulation was further diluted to 2.5 g / L.

[0049] Comparative Example B was formed as Example 1, except that the first dispersion was used instead of the second dispersion. In forming Comparative Example A, the polyolefin dispersion was 52.5 weight percent solids and had a volume average particle size of 337 nanometers.

[0050] For Comparative Example B, a polyethylene-polyvinyl acetate copolymer was used. The polyethylene-polyvinyl acetate copolymer, THURICIDE TM and water to include 2.5 wt% of the copolymer, and the resulting formulation was further diluted to 2.5 g / L.

[0051] For Comparative Example C, neither the first dispersion nor the second dispersion was used; THURICIDE TM Dilute to 2.5 g / L.

[0052] The residual protein concentration and Bacillus thuringiensis activity of Example 1 and Comparative Examples A to C were determined as follows.

[0053] Parafilm sheets (2 inches by 4 inches) were placed on black Leneta cards, and Kimwipes were gently rubbed on the parafilm before removing the parafilm paper. 15 drops (15 μL to 30 μL) of Example 1 and Comparative Examples A to C were randomly placed on the corresponding parafilm in an array using an automatic pipette, with one parafilm used for each example / comparative example; the samples were vortexed between each group of 5 drops to maintain the consistency of the composition. The parafilm was then dried in an incubator at about 28°C for about 1 hour.

[0054] The dried parafilms were then subjected to simulated rainfall as follows. Each dried parafilm was placed individually in an ExoTerra Monsoon RS400 Rainfall System (equipped with 2 Exo Terra standard nozzles without any extensions); the parafilm was 13 inches from the spray nozzle. Water was sprayed on the parafilm at a flow rate of 1.5 liters / hour and measured at the substrate interface for 5 minutes; afterward, the parafilm was allowed to dry.

[0055] After exposure to simulated rainfall, the samples were extracted. For extraction, each of the corresponding parafilms was cut so that each point generated by the drop was centered at about 0.25 square inches. For each corresponding parafilm, all cut dotted squares were placed in a glass vial, to which a sodium lauryl sulfate solution (1 ml, 2 weight percent sodium lauryl sulfate in water) was added. Each glass vial was then sonicated and soaked for about 8 hours. The sonication was repeated three times for extraction.

[0056] Residual protein concentration was determined by bicinchoninic acid assay (BCA) as follows. TMBCA Protein Assay Reagent A and PIERCE TM BCA protein assay reagent B (both can be purchased from Thermo Scientific TM ) is to combine reagent A (2 ml) and reagent B (40 μl) to form a reagent mixture.

[0057] One hundred (100) microliters of each extraction sample (Extraction Example 1 and Comparative Examples A to C) was placed in a corresponding cuvette; then the reagent mixture (2 milliliters) was added to each cuvette; and then the cuvette was incubated at 30° C. for about 2 hours. The residual protein concentration was determined using the absorbance determined at 562 nm using a Cary 100 UV-Visible spectrophotometer. The results are reported in Table 1.

[0058] Table 1

[0059]

[0060]

[0061] The data in Table 1 illustrate that Example 1 has an improved (ie, greater) residual protein concentration compared to each of Comparative Examples A-C.

[0062] Use 0.1 wt% TWEEN TM The solutions of Example 1 and Comparative Examples A to C extracted as above were diluted to the desired starting concentrations and then serially diluted and plated at appropriate concentrations. The resulting Bacillus thuringiensis activities are reported in Table 2.

[0063] Table 2

[0064]

[0065] The data in Table 2 illustrate that each of Example 1 and Comparative Examples A to B had a Bacillus thuringiensis activity retention percentage of greater than 80%.

Claims

1. A pest control composition, comprising: A plurality of composite particles, each of the composite particles comprising: A polyolefin core, wherein the polyolefin of the polyolefin core has 50 wt% or more of monomer structural units derived from olefin monomers based on the total weight of the polyolefin; and a plurality of monomer structural units derived from vinyl monomers polymerized onto the polyolefin core, wherein the vinyl monomers include one or more (meth)acrylic monomers; Bacillus thuringiensis; and water.

2. The pest control composition according to claim 1, wherein the composite particle is 0.1 wt% to 15.0 wt% of the composition based on the total weight of the combination of the composite particle, the Bacillus thuringiensis and the water.

3. The pest control composition according to any one of claims 1 to 2, wherein the polyolefin core of the composite particle comprises an ethylene / octene copolymer.

4. The pest control composition according to any one of claims 1 to 3, wherein the water is 20.00 wt% to 99.89 wt% of the composition based on the total weight of the combination of the composite particles, the Bacillus thuringiensis and the water. 5 . The pest control composition according to claim 1 , wherein the composite particles have a weight ratio of the polyolefin core to the monomer structural unit derived from the vinyl monomer of 90:10 to 60:

40. 6 . The pest control composition according to claim 5 , wherein the composite particles have a weight ratio of the polyolefin core to the monomer structural unit derived from the vinyl monomer of 80:

20.

7. The pest control composition according to any one of claims 1 to 6, wherein the polyolefin core is cross-linked.

Images