Delivery particles based on amine-thiol-ene conjugates and derivatives

Abstract

Improved delivery particles comprising a benefit agent core material and a shell encapsulating the core material are described, as well as methods and articles of manufacture to form such delivery particles. The shell is the reaction product: an ATEC (amine-thiol ene) conjugate that can be further reacted with one or more multifunctional (meth) acrylates or isocyanates, or both. The delivery particles of the present invention have improved release properties, and embodiments exhibit enhanced degradation properties in the OECD test method 301B.

Description

Field of the Invention

[0001] The present invention relates to a capsule manufacturing method and a biodegradable delivery particle produced by such a method, the delivery particle comprising a core material and a shell encapsulating the core.

[0002] Related technical description

[0003] Microencapsulation is a method in which a droplet of a liquid, a solid particle or a gas is encapsulated in a solid shell and usually within the micrometer range. The core material is separated from the surrounding environment by a shell. Microencapsulation technology has a wide range of commercial applications for different industries. Generally speaking, capsules can carry out one or more of the following: (i) providing the stability of formulations or materials via mechanical separation of incompatible components, (ii) protecting the core material from the surrounding environment, (iii) masking or hiding the undesirable properties of active ingredients, and (iv) controlling or triggering the release of active ingredients to a specific time or position. All these attributes can lead to an increase in the shelf life of several products and the stability of active ingredients in liquid formulations.

[0004] Various processes and exemplary methods and materials for microencapsulation are described in Schwantes (U.S. Patent No. 6,592,990), Nagai et al. (U.S. Patent No. 4,708,924), Baker et al. (U.S. Patent No. 4,166,152), Wojciak (U.S. Patent No. 4,093,556), Matsukawa et al. (U.S. Patent No. 3,965,033), Ozono (U.S. Patent No. 4,588,639), Irgarashi et al. (U.S. Patent No. 4,610,927), Brown et al. (U.S. Patent No. 4,552,811), Scher (U.S. Patent No. 4,285,720), Jahns et al. (U.S. Patent Nos. 5,596,051 and 5,292,835), Matson (U.S. Patent No. 3,516,941), Foris et al. (U.S. Patent Nos. 4,001,140, ​​4,087,376, 4,089,802 and 4,100,103), Greene et al. (U.S. Patent Nos. 2,800,458, 2,800,457 and 2,730,456), Clark (U.S. Patent No. 6,531,156), Hoshi et al. (U.S. Patent No. 4,221,710), Hayford (U.S. Patent No. 4,444,699), Hasler et al. (U.S. Patent No. 5,105,823), Stevens (U.S. Patent No. 4,197,346), Riecke (U.S. Patent No. 4,622,267), Greiner et al. (U.S. Patent No. 4,547,429), and Tice et al. (U.S. Pat. No. 5,407,609) et al. and as taught by Herbig in the section entitled "Microencapsulation" in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 16, pp. 438-463.

[0005] Core-shell encapsulation can be used to preserve active materials (e.g., beneficial agents) in harsh environments and release them at a desired time, which may be during or after use of the article into which the encapsulate is incorporated. Among the various mechanisms that can be used to release beneficial agents from the encapsulate, the mechanism that is typically relied upon is mechanical rupture of the capsule shell by friction or pressure. The choice of mechanical rupture as a release mechanism poses another challenge to manufacturers because rupture must occur at a specific desired time, even if the capsule is subjected to mechanical stress before the desired release time.

[0006] Industrial interest in encapsulation technology has led to the development of several polymer capsule chemistries that attempt to meet the requirements of biodegradability, low shell permeability, high deposition, targeted mechanical properties and rupture profiles. Increased environmental concerns have put polymer capsules under scrutiny, so manufacturers have begun to investigate sustainable solutions for the encapsulation of beneficial agents.

[0007] Biodegradable materials exist and can be formed into delivery particles via coacervation, spray drying or phase inversion precipitation. However, delivery particles formed using these materials and techniques are highly porous and are not suitable for aqueous compositions containing surfactants or other carrier materials because the beneficial agent is released prematurely into the composition.

[0008] There are non-leaky and functional delivery particles in surfactant-based aqueous compositions, however due to their chemical nature and cross-linking they are not biodegradable.

[0009] Encapsulation can be found in a variety of fields such as pharmaceuticals, personal care, textiles, food, coatings and agriculture. In addition, the main challenge faced by encapsulation is the need to completely retain the encapsulated active substance within the capsule throughout the supply chain until the controlled or triggered release of the core material is applied. Especially when it comes to small molecule encapsulation, there are significantly limited microencapsulation technologies that can meet the stringent standards of long-term retention and active protection capabilities for commercial needs.

[0010] There is a need for delivery particles with high structural integrity, thereby reducing leakage and resisting damage from harsh environments.Variations of such delivery particles that can be designed to be biodegradable as taught herein would address the issue of sustainability.

[0011] definition

[0012] As used herein, reference to the term "(meth)acrylate" or "(meth)acrylic" will be understood to refer to both acrylate and methacrylate forms of the specified monomer, oligomer and / or prepolymer (e.g., "isobornyl (meth)acrylate" means that both isobornyl methacrylate and isobornyl acrylate are possible, similarly, reference to alkyl (meth)acrylates means that both alkyl acrylates and alkyl methacrylates are possible, and similarly, poly (meth)acrylates means that both polyacrylates and polymethacrylates are possible). Similarly, use of the phrase "prepolymer" means that the material mentioned can exist as a prepolymer or a combination of oligomers and prepolymers. Similarly, it is understood that references to one or more (meth)acrylates in general herein, such as "water-soluble (meth)acrylates", "aqueous (meth)acrylates", etc., are intended to cover or include (meth)acrylate monomers and / or oligomers. Additionally, when referring to certain (meth)acrylate monomers and / or oligomers or initiators, the descriptors "water-soluble or water-dispersible," "water-soluble" or "water-dispersible" mean that the specified components are soluble or dispersible in a given matrix solution alone or in the presence of a suitable solubilizer or emulsifier, or when a certain temperature and / or pH is reached.

[0013] Unless otherwise indicated, each alkyl moiety herein may be C1-C8, or even C1-C 24Poly(meth)acrylate materials are intended to include a wide range of polymeric materials including, for example, polyester poly(meth)acrylates, urethane and polyurethane poly(meth)acrylates (especially those prepared by the reaction of hydroxyalkyl (meth)acrylates with polyisocyanates or urethane polyisocyanates), methyl cyanoacrylate, ethyl cyanoacrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, allyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylate functionalized silicones, di-, tri- and tetra-ethylene glycol di(meth)acrylates. In some embodiments, the present invention relates to acrylates, dipropylene glycol di(meth)acrylates, polyethylene glycol di(meth)acrylates, di(pentamethylene glycol) di(meth)acrylates, ethylene di(meth)acrylates, neopentyl glycol di(meth)acrylates, ethoxylated bisphenol A di(meth)acrylates, bisphenol A di(meth)acrylates, diglycerol di(meth)acrylates, tetraethylene glycol dichloroacrylates, 1,3-butylene glycol di(meth)acrylates, neopentyl di(meth)acrylates, polyethylene glycol di(meth)acrylates and dipropylene glycol di(meth)acrylates as well as various multifunctional (meth)acrylates and multifunctional amine (meth)acrylates. Monofunctional acrylates (i.e., those containing only one acrylate group) can also be used advantageously. Typical monoacrylates include 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, cyanoethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, p-dimethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, chlorobenzyl (meth)acrylate, aminoalkyl (meth)acrylate, various alkyl (meth)acrylates, and glycidyl (meth)acrylate. Of course, mixtures of (meth)acrylates or their derivatives and combinations of one or more (meth)acrylate monomers, oligomers and / or prepolymers or their derivatives with other copolymerizable monomers (including acrylonitrile and methacrylonitrile) may also be used. Multifunctional (meth)acrylate monomers will typically have at least two, at least three, and preferably at least four, at least five, or even at least six polymerizable functional groups.

[0014] For ease of reference in this specification and claims, the terms "monomer" or "monomers" as used herein with respect to the structural material forming the wall polymer of the delivery particle are to be understood as monomers, but also include oligomers and / or prepolymers formed from the specified monomers.

[0015] As used herein, the term "water-soluble material" means a material having a solubility of at least 0.5 wt% in water at 60°C.

[0016] As used herein, the term "oil-soluble" means a material having a solubility of at least 0.1 wt% in the core of interest at 50°C.

[0017] As used herein, the term "oil dispersible" means a material that is dispersible at least 0.1 wt% in a core of interest at 50°C without visible agglomerates.

[0018] As used herein, the terms "delivery particle" and "microcapsule" or "encapsulate" are used interchangeably. "Wall material" or "shell" are also used interchangeably to refer to the shell of the delivery particle. "Beneficial agent" or "core" are used interchangeably to refer to the contents encapsulated within the delivery particle. Summary of the invention

[0019] The present invention describes a delivery particle comprising a core material and a shell encapsulating the core material. The core material may comprise a beneficial agent. The shell comprises a polymer. More particularly, the polymer comprises a reaction product: an amine-thiol-ene conjugate.

[0020] In alternative embodiments, the amine-thiol-ene conjugate is additionally cross-linked with one or more of the following

[0021] Multifunctional (meth)acrylate; or

[0022] Isocyanate.

[0023] Articles of manufacture based on such delivery of particles are also described.

[0024] Detailed Description

[0025] The present invention describes a novel delivery particle. The delivery particle comprises a core material and a shell encapsulating the core material. The core material comprises a beneficial agent. The shell comprises a polymer. More particularly, the polymer comprises a reaction product: an amine-thiol-ene conjugate.

[0026] The conjugate may additionally be further crosslinked with one or more of a multifunctional (meth)acrylate or isocyanate, as more fully described herein.

[0027] In an embodiment, the amine of the amine-thiol-ene conjugate ("ATEC") that forms the shell of the delivery particle is a monoalkyl diamine or a dialkyl diamine, or a monoalkyl triamine or a dialkyl triamine. The amine may be a primary amine, and may include, by way of illustration and not limitation, furfurylamine, allylamine, dimethylene diamine, n-butylamine, octylamine, propylamine, ethylamine, benzylamine. As described more fully herein and in the Examples, the amines useful in the amine-thiol-ene conjugate are aliphatic amines and primary amines having electron withdrawing groups. Secondary amines may be used for further reaction of the amine-thiol-ene conjugate with acrylates. Multifunctional amines may be used to introduce additional side chain reactive groups. The electron withdrawing group may include a nitro group (-NO2), an aldehyde group (-CHO), a keto group (-C=OR), a cyano group (-CN), a carboxyl group (-COOH), or an ester group (-COOR).

[0028] In more specific embodiments, the thiol of the amine-thiol-ene conjugate is a thiolactone. The thiolactone ring may typically have a 3-8 ring, consisting of a thiol group and a carbon. The thiolactone ring may be substituted by an amine group (e.g., a primary amine). The thiolactone may comprise homocysteine ​​thiolactone or acetylated homocysteine ​​thiolactone.

[0029] The olefin portion of the amine-thiol-ene conjugate is an unsaturated compound and can be selected from a vinyl compound or an acrylate. In an embodiment, when a vinyl compound is selected as the olefin portion of the amine-thiol-ene conjugate, the vinyl compound advantageously includes a functional group comprising an electron withdrawing group. The olefin is an unsaturated compound having an olefinic bond, and the addition of the olefin to the conjugate is carried out via the olefinic bond. The molar ratio of the amine to the thiol to the olefinic moiety in the conjugate is 0.75 / 1 / 1.25 to 1.25 / 1 / 0.75, preferably 0.85 / 1 / 1.15 to 1.15 / 1 / 0.85, more preferably 0.95 / 1 / 1.05 to 1.05 / 1 / 0.95.

[0030] By further combination, the amine-thiol-ene conjugate may further comprise a free radical cross-linking reaction product of the amine-thiol-ene conjugate with one or more of a multifunctional (meth)acrylate and an isocyanate. For the sake of clarity, the amine-thiol-ene conjugate may further react with a multifunctional (meth)acrylate or may react with an isocyanate or may react with both, so that the shell polymer design of the delivery particle has diversity.

[0031] The amine-thiol-ene conjugate reacted with the isocyanate can be further cross-linked with a multifunctional (meth)acrylate free radical. In a variant, the amine-thiol-ene conjugate can be further reacted and can additionally form a reaction product of the amine-thiol-ene conjugate with either or even both of the isocyanate or the multifunctional (meth)acrylate. This allows for considerable diversity in the assembly of polymers for specific purposes. In an embodiment, the multifunctional (meth)acrylate is present in a molar excess compared to the thiolactone and the amine.

[0032] The amine-thiol-ene conjugate may comprise an additional cross-linked reaction product of the amine-thiol-ene conjugate with one or more of the isocyanates, or a Michael adduct comprising a multifunctional (meth)acrylate, or one or more of the aza-Michael adduct comprising a multifunctional acrylate. In various alternatives, the amine-thiol-ene conjugate may constitute a minor or major component of the polymer, desirably accounting for at least 50% by weight of the shell composition. Advantageously the amine-thiol-ene conjugate may be either the sole polymer (100%) or may be combined with a portion of one or more of the isocyanates or (meth)acrylates as a blend. In alternative embodiments, the isocyanates and / or methacrylates form 0-10%, or even 0-25%, or even 0-50%, or even 15-50% of the polymer.

[0033] The delivery particle comprises a core material and a shell encapsulating the core material, wherein the core material comprises a beneficial agent, and wherein the shell comprises a polymer comprising an amine, a thiol lactone, a multifunctional (meth) acrylate, and a reaction product of a multifunctional. In embodiments, it is understood that additional combinations can be assembled by adding a single isocyanate, a single (meth) acrylate, or a combination of both to further react the amine thiol ene conjugate.

[0034] In an embodiment, the amine-thiol-ene conjugate is a reaction product of an alkylamine, a 3-, 4-, 5- or 6-membered thiolactone (preferably a 4-, 5- or 6-membered thiolactone) and a vinyl compound having an electron withdrawing group. Delivery particle composition, wherein the amine in the ATEC conjugate is an alkylamine, and the alkyl moiety can be selected from a 3-18 carbon alkyl moiety. The electron withdrawing substituent on the vinyl compound can include any of a nitro group (NO2), an aldehyde group (-CHO), a keto group (-C=OR), a cyano group (-CN), a carboxyl group (-COOH) or an ester group (-COOR).

[0035] In the delivery particle composition, the (meth)acrylate may be a multifunctional (meth)acrylate and may be selected from oil-soluble (meth)acrylates selected from difunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, pentafunctional (meth)acrylates, hexafunctional (meth)acrylates, heptafunctional (meth)acrylates, octafunctional (meth)acrylates and mixtures thereof.

[0036] Optionally, the multifunctional (meth)acrylate is selected from water-soluble or water-dispersible (meth)acrylates independently selected from 2-carboxyethyl acrylate, 2-carboxyethyl acrylate oligomers, 2-carboxypropyl acrylate, 4-acryloyloxyphenylacetic acid, carboxyoctyl acrylate, tripropylene glycol diacrylate, ethoxylated bisphenol diacrylate, dipropylene glycol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol triacrylate, dimethoxyl alcohol ... Tetraol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol tri(meth)acrylate, ethylene glycol diacrylate, di-, tri-, tetra- or pentaethylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth)acrylate, cyanoethyl acrylate, 2-hydroxypropyl acrylate, lauryl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl chloride acrylate, aminoalkyl acrylate, ethylaminoethyl (meth)acrylate, aminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, diethylamino (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, or a combination of the foregoing.

[0037] The core constitutes the material encapsulated by the microcapsule. Typically, particularly when the core material is a liquid material, the core material and the composition forming the inner wall of the microcapsule or one or more of the solvents for the beneficial agent or the distribution modifier merge. If the core material can play the role of an oil solvent in the capsule, such as acting as a solvent or carrier for a wall-forming material or a beneficial agent, the core material can be made to become the encapsulated main material, or if the carrier itself is a beneficial agent, it can be the encapsulated whole materials. However, often, the beneficial agent is 0.01-99 weight percent of the capsule internal content, preferably 0.01-about 65 weight % of the capsule internal content, and more preferably 0.1-about 45 weight % of the capsule internal content. For some applications, even if only trace amounts, the core material can also be effective.

[0038] When the benefit agent itself is not sufficient to act as an oil phase or solvent, particularly for wall-forming materials, the oil phase may comprise a suitable carrier and / or solvent. In this sense, the oil is optional, as the benefit agent itself may sometimes be an oil. These carriers or solvents are typically oils, preferably having a boiling point greater than about 80° C. and having low volatility and being non-flammable. Although not limited thereto, they preferably comprise one or more esters (preferably with a chain length of up to 18 carbon atoms or even up to 42 carbon atoms) and / or triglycerides such as esters of C6-C12 fatty acids and glycerol. Exemplary carriers and solvents include, but are not limited to, ethyl diphenylmethane; isopropyl diphenylethane; butyl diphenylethane; benzyl xylene; alkyl biphenyls, such as propyl biphenyl and butyl biphenyl; dialkyl phthalates, such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, and ditridecyl phthalate; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; alkyl benzenes, such as dodecylbenzene; alkyl or aralkyl benzoates, such as benzyl benzoate; diaryl ethers; di(aralkyl) ethers and aryl aralkyl ethers; ethers, such as diphenyl ether , dibenzyl ether and phenylbenzyl ether; liquid higher alkyl ketones (having at least 9 carbon atoms); alkyl or aralkyl benzoates, such as benzyl benzoate; alkylated naphthalene, such as dipropylnaphthalene; partially hydrogenated terphenyls; high boiling straight or branched hydrocarbons; alkylaryl hydrocarbons, such as toluene; vegetable oils and other crop oils, such as rapeseed oil, soybean oil, corn oil, sunflower oil, cottonseed oil, lemon oil, olive oil and pine oil; methyl esters of fatty acids derived from the transesterification of vegetable oils and other crop oils, methyl esters of oleic acid, esters of vegetable oils, such as soybean methyl esters, straight-chain paraffin aliphatic hydrocarbons and mixtures of the foregoing. In some embodiments, the benefit agent constituting the core is a fragrance, not by way of limitation, but preferably a fragrance comprising a fragrance raw material characterized by a logP of about 2.5 to about 4.5. The core may additionally comprise a partition modifier selected from the group consisting of isopropyl myristate, vegetable oils, modified vegetable oils, monoesters, diesters and triesters of C4-C24 fatty acids, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, preferably isopropyl myristate. Although illustrated here with fragrances, other benefit agents (e.g., agricultural actives) as more fully described in this specification may comprise the core having the polymer shell of the present invention.

[0039] In some embodiments, the wall has a biodegradability of greater than 30% CO2, preferably greater than 40% CO2, more preferably greater than 50% CO2, even more preferably greater than 60% CO2 within 60 days following the OECD 301B test.

[0040] Optionally or alternatively, the wall of the delivery particle further comprises a coating material, preferably wherein the coating material is selected from the group consisting of poly(meth)acrylates, poly(ethylene-maleic anhydride), polyamines, waxes, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone-vinyl acrylate, polyvinylpyrrolidone methacrylate, polyvinylpyrrolidone / vinyl acetate, polyvinyl acetal, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone-vinyl acrylate, polyvinylpyrrolidone-methacrylate, polyvinylpyrrolidone-vinyl acetate, polyvinylpyrrolidone-vinyl acetal ...acrylate, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone-vinyl acrylate, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone-vinyl acrylate, polyvinylpyrrolidone-vinyl acetal, polyvinylpyrrolidone-vinyl acetal, polyvinyl acetal), polyvinyl butyral, polysiloxane, poly(propylene maleic anhydride), maleic anhydride derivatives, copolymers of maleic anhydride derivatives, polyvinyl alcohol, styrene-butadiene latex, gelatin, gum arabic, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, other modified celluloses, sodium alginate, chitosan, chitin, casein, pectin, modified starch, polyvinyl acetal, polyvinyl butyral, polyvinyl methyl ether / maleic anhydride, polyvinyl pyrrolidone and its copolymers, poly(vinyl pyrrolidone / methacrylamidopropyltrimethylammonium chloride), polyvinyl pyrrolidone / vinyl acetate, polyvinyl pyrrolidone / dimethylaminoethyl methacrylate, polyvinyl amine, polyvinyl formamide, polyallylamine, copolymers of polyvinyl amine, and mixtures thereof.

[0041] The present invention also describes a method of forming a population of delivery particles, the delivery particles comprising a core material and a shell encapsulating the core material, wherein the core material comprises a beneficial agent; and wherein the shell comprises a polymer, the polymer comprising the reaction product:

[0042] The method includes:

[0043] The delivery particles have a leakage of less than about 50% as determined by the Leakage Test described in the Test Methods section.

[0044] In other configurations, the delivery particles of the present invention can be made into new articles by incorporating into various articles. Such articles can be selected from agricultural formulations, slurries encapsulating agricultural active substances, populations of dried microcapsules encapsulating agricultural active substances, agricultural formulations encapsulating pesticides, and agricultural formulations for delivering pre-emergence herbicides. Agricultural active substances can be selected from agricultural herbicides, agricultural pheromones, agricultural pesticides, agricultural nutrients, insect control agents, and plant stimulants.

[0045] Detailed Description

[0046] The present invention describes a delivery particle comprising a core material and a shell encapsulating the core material. The core material may comprise a beneficial agent. The shell comprises a polymer. More particularly, the polymer comprises a reaction product: an amine-thiol-ene conjugate (ATEC), and in addition the ATEC conjugate is cross-linked with one or more of the following

[0047] i) multifunctional (meth)acrylate; or

[0048] ii) Isocyanates.

[0049] More particularly, the delivery particle shell comprises a polymer. The polymer comprises an amine-thiol-ene conjugate, which is a reaction product of an amine, a thiol lactone, and an ene compound, and in an embodiment, the thiol-ene conjugate is further reacted with one or more of a multifunctional methacrylate and a multifunctional isocyanate or both. In the invention, a combination of more than one multifunctional methacrylate or more than one multifunctional isocyanate can be used to customize the polymer of the delivery particle shell.

[0050] Capsules have been successfully prepared using ATEC conjugates alone as polymers. However, by further crosslinking with isocyanates or with acrylate monomers and prepolymers, encapsulates can be formed with tailored properties that advantageously benefit from the properties of the chosen constituent monomers or prepolymers.

[0051] Amine-thiol-ene (ATEC) reaction can be accomplished by the following: primary amine groups react with thiolactone compounds, opening the thiolactone ring and generating amide bonds and reactive thiol groups. The reactive thiol groups formed further undergo Michael addition with vinyl groups (e.g., with acrylate groups) to form repeating units (amide / thiol / ester) of polymers. Thiolactones are four to eight-membered rings, the most common four-membered, five-membered, and six-membered rings, such as represented by β, γ, and δ thiolactones. γ and δ, 5- and 6-membered ring thiolactones can be used for polymer synthesis, respectively. The cleavage of the thiol ring by reacting with a nucleophilic agent leads to ring opening via nucleophilic addition-elimination. Nucleophiles used for ring opening in alkaline conditions may include water, alcohols, and amines, wherein amines are more favorable because aminolysis does not require additives. γ thiolactones may include homocysteine-γ-thiolactone or α-amino-γ-thiobutyrolactone. Aminolysis of γ-thiolactone can be used to produce derivatives such as N-acetylhomocysteine ​​thiolactone or α-isocyanato-γ-thiolactone, or N-(2-alkylacetyl)homocysteine ​​thiolactone. Isocyanato-lactone can be converted into carbamate, urea and semicarbazide in the presence of alcohol, amine or hydrazine.

[0052] The thiolactone ring opening is achieved in the case of reaction with a nucleophile. Primary amines are particularly nucleophilic and can be used for this purpose. Enolates formed by abstraction of the α-hydrogen by a strong base are also nucleophiles. Available nucleophiles can include amines as well as enolates. The amine thiol ene conjugate reaction is attractive because it generally requires very mild conditions to occur. The formation of the enolate can include harsher conditions, which can also potentially drive competing reactions, such as Michael additions with ene compounds.

[0053] The thiol group that can be obtained from the cleavage of the thiolactone reacts with an unsaturated group, such as a vinyl or acrylate group. The reaction of the thiol group with the unsaturated group can be carried out by a free radical mediated thiol-acrylate reaction or a thiol acrylate Michael addition.

[0054] Cleavage of thiolactones in the presence of an alkylating agent under alkaline conditions can produce alkylated thiolactones. Alkylation of thiol groups can produce alkylated homocysteine ​​derivatives. By sequential hydrolysis and conjugate addition, for example, γ-thiobutyrolactone and propiolic acid produce the corresponding acrylic acid under alkaline conditions. Aminolysis is preferred over alcoholysis and hydrolysis because no additives are required. Aminolysis allows the introduction of functional groups in the reaction product via amines.

[0055] Aminolysis of the thiolactone coupled with addition of the resulting thiol to an unsaturated group (eg, vinyl) produces an amine-thiol-ene conjugate. The resulting thiol can be added to the unsaturated group either by a free radical process or by nucleophilic addition.

[0056] Amines useful in amine-thiol-ene conjugates are aliphatic amines and primary amines with electron withdrawing groups. Secondary amines can be used for further reaction of amine-thiol-ene conjugates with acrylates. Multifunctional amines can be used to introduce additional side chain reactive groups. Electron withdrawing groups can include nitro (-NO2), aldehyde (-CHO), keto (-C=OR), cyano (-CN), carboxyl (-COOH) or ester (-COOR).

[0057] If a multifunctional primary amine and a multifunctional acrylate are used as reactants in the ATEC conjugate, high molecular weight polymers can be prepared. Additionally, if a molar excess of acrylate functionality is used in the conjugate, the ATEC polymer can include residual acrylate groups that can be further polymerized. After the amine-thiol-ene conjugate ("ATEC conjugate") is formed, further reaction of the ATEC conjugate with either or both of the isocyanate and acrylate moieties can produce a tailored polymer.

[0058] Acrylate moieties that are olefinically unsaturated in forming the conjugates can undergo aza-Michael addition with primary amines. Additional reactions of the ATEC conjugates with remaining or additional unsaturated groups (eg, acrylate or methacrylate) can be performed by free radical mediated reactions or Michael additions.

[0059] The reaction can proceed via the thiol group after ring opening, or in the presence of a strong base (for the remaining portion of the adduct), the Michael donor can be deprotonated to form an anion that can react with the acrylate double bond and can be used to regenerate the base. The adduct formed can even undergo a second, albeit slower, Michael addition. Michael donors include various amines, enolates, and thiols and even phosphines. Michael acceptors will include methacrylates, (meth)acrylamides, maleimides, acrylonitrile, and cyanoacrylates.

[0060] The following sequence schematically shows the assembly of ATEC conjugates that may be used in the encapsulation of the present invention, and these are further described in the Examples.

[0061]

[0062] Or alternatively, the amine can be a diamine and the thiolactone can be homocysteine ​​thiolactone and the acrylate can be polyethylene glycol diacrylate, as shown below:

[0063]

[0064] The ATEC conjugate can be further reacted with an isocyanate or (meth)acrylate. For example, any remaining or additional unsaturated groups (e.g., acrylate or methacrylate) can be reacted by free radical mediated reaction or Michael addition with the formed ATEC conjugate. Amines on the ATEC conjugate can be used as reaction sites with (meth)acrylates. Acrylates can also undergo Michael addition with any remaining amine groups of the ATEC conjugate. Isocyanates will also bond with any remaining primary amine groups. Primary amines are generally more reactive than secondary amines. Reaction with carboxylic acids can be used to form the corresponding amides.

[0065] In forming the ATEC conjugates, the following thiolactones are illustrative:

[0066] β, γ and δ thiolactones

[0067] and more specifically, α-thiolactone (n=0), β-thiolactone (n=1), γ-thiolactone (n=2), and δ-thiolactone (n=3),

[0068]

[0069] More specific examples of thiolactones that can be used to form ATEC conjugates are:

[0070] DL-N-Acetylhomocysteine ​​Thiolactone

[0071] DL-Homocysteine ​​Thiolactone Hydrochloride

[0072] γ-Thiobutyrolactone

[0073] L-Homocysteine ​​Thiolactone Hydrochloride

[0074] 2(5H)-Thiophenone

[0075] Erdosteine

[0076]

[0077] In forming the ATEC conjugates, the following amines are illustrative:

[0078] Hexamethylenediamine H2NCH2(CH2)4CH2NH2

[0079] Ethylenediamine

[0080] Octamethylenediamine, 1,8-octanediamine H2NCH2(CH2)6CH2NH2

[0081] Diethylenetriamine

[0082] Bis(hexamethylene)triamine

[0083] Tetraethylenepentylamine

[0084] 1,3-Diaminopentane, 1,3-pentanediamine

[0085] Pentaethylenehexylamine

[0086]

[0087] Triethylenetetramine

[0088] 2-Methyl-1,5-pentanediamine, 2-methylpentanediamine

[0089]

[0090] 1,5-Diaminopentane, 1,5-pentanediamine, pentamethylenediamine

[0091]

[0092] 1,4-Diaminobutane, 1,4-diaminobutane, putrescine, tetramethylenediamine

[0093]

[0094] Butane-2,3-diamine dihydrochloride

[0095] Cyclopentane-1,2-diamine 2HCl

[0096]

[0097] Pentane-2,4-diamine dihydrochloride

[0098] Cycloheptane-1,4-diamine dihydrochloride

[0099] 3,6,9,12-Tetraoxatetradecane-1,14-diamine

[0100]

[0101] 3,6,9,12,15-pentaoxaheptadecan-1,17-diamine

[0102]

[0103] 3,6,9,12,15,18,21,24,27,30-Decaoxatriacontane-1,32-diamine

[0104] Hex-5-ene-1,2-diamine

[0105]

[0106] But-2-yne-1,4-diamine dihydrochloride

[0107] 2-Methylbutane-2,3-diamine dihydrochloride

[0108] 4-Methoxybutane-1,2-diamine dihydrochloride

[0109]

[0110] 4-Methylpentane-1,2-diamine dihydrochloride

[0111]

[0112] (2E)-But-2-ene-1,4-diamine

[0113] 2-Fluoropropane-1,3-diamine dihydrochloride

[0114] 2-Methylpropane-1,3-diamine dihydrochloride

[0115] 3-Methylbutane-1,3-diamine dihydrochloride

[0116] 3,3-Dimethylbutane-1,2-diamine dihydrochloride

[0117] 2,7-Dimethyloctane-2,7-diamine dihydrochloride

[0118]

[0119] 4,4-Dimethylpentane-1,2-diamine dihydrochloride

[0120]

[0121] 1-Cyclobutylethane-1,2-diamine dihydrochloride

[0122]

[0123] Poly(ethylene glycol) diamine

[0124] N1-(3-(3-aminopropylamino)propyl)butane-1,4-diamine 4HCl

[0125]

[0126] Spermine

[0127]

[0128] 1,3-Diamino-2-propanol

[0129] N,N'-Bis(2-aminoethyl)-1,3-propanediamine

[0130]

[0131] {3-[Bis(3-aminopropyl)amino]propyl}dimethylamine

[0132]

[0133] (4-Amino-3-fluorobutyl)(3-aminobutyl)amine

[0134]

[0135] N-(4-Aminobutyl)-1,4-butanediamine 3HCl

[0136]

[0137] H2N-PEG9-CH2CH2NH2

[0138]

[0139] Amino-PEG13-amine

[0140]

[0141] 1,19-Diamino-4,7,10,13,16-pentaoxanonadecane

[0142]

[0143] H2N-PEG6-CH2CH2NH2

[0144]

[0145] Amino-PEG8-amine

[0146]

[0147] Amino-PEG11-amine

[0148]

[0149] N1,N1-Bis(3-aminopropyl)propane-1,3-diamine

[0150]

[0151] 3-(2-Aminoethyl)pentane-1,5-diamine

[0152] 3-Methoxy-2-methylpropane-1,2-diamine

[0153] 2-(Aminomethyl)-2-methylpropane-1,3-diamine

[0154] 3-(2-Aminoethyl)pentane-1,5-diamine

[0155] 2-Methylpropane-1,2-diamine dihydrochloride

[0156] 2,3-Dimethylbutane-2,3-diamine dihydrochloride

[0157] 3-Ethylpentane-1,3-diamine dihydrochloride

[0158] 2-Methylpentane-1,2-diamine

[0159] 2,2,4,4-Tetramethylcyclobutane-1,3-diamine

[0160] 2,3-Dimethylbutane-1,2-diamine

[0161] 2,3-Dimethylbutane-2,3-diamine

[0162] 2,4-Dimethylpentane-1,2-diamine

[0163] 4-Methylpentane-1,2-diamine

[0164] 4-Methylpentane-1,4-diamine

[0165] 2-Dimethoxypropane-1,3-diamine

[0166] Cyclopentane-1,2-diamine

[0167] Pentane-2,4-diamine

[0168] Hexane-2,5-diamine

[0169] Hexane-1,2-diamine

[0170]

[0171] Pentane-1,3,5-triamine trihydrochloride

[0172] Propane-1,2,3-triamine

[0173] 5-aminopentanimidamide dihydrochloride

[0174]

[0175] 3-aminopropanimidamide dihydrochloride

[0176]

[0177] 2-aminoethanimidamide dihydrochloride

[0178]

[0179] Tris(2-aminoethyl)amine

[0180] As a non-limiting illustration of how to produce the delivery particles of the present invention, when the reaction is stoichiometric, one mole of EDA (two moles of amine) is reacted with two moles of HCTL and one mole of SR610 (two moles of acrylate) for the complete reaction. In order to have residual acrylate groups for additional free radical polymerization, a 10% molar excess of acrylate, such as SR610 (1.1 moles, containing 2.2 moles of acrylate) can be used.

[0181] Polymerization process:

[0182] The initial polymer solution can be prepared as a 20% solution in water. Use a magnetic stirring bar to mix water in a glass beaker. Add and dissolve the acrylate, then add the HCTL. Finally, add an amine (e.g., EDA) dropwise to the beaker under continuous stirring. The solution is mixed at room temperature for 24 hours to allow complete curing. After 24 hours, the solution pH is typically about 5.4. Ammonia is added to adjust the pH to alkaline, for example to about 8, and additional mixing is completed to allow additional curing. Additional curing time at elevated pH enables any primary amine reactant species present to react further.

[0183] Acidic HCTLs lower solution pH. After room temperature cure, the batch was opaque white, but after pH adjustment and further cure, the solution with these particular materials was slightly clear and had a pink / tan hue.

[0184] The next step in the process is to combine the above ATEC polymer (the hydrophilic portion of the surfactant polymer) with additional (meth)acrylates (e.g., multifunctional methacrylates such as (tert-butylaminoethyl methacrylate, TBEAMA)), which can form reactive sites for the addition of isocyanate groups.

[0185] The volume weighted median particle size of delivery particles according to the invention may range from about 1 micron to about 150 microns, or even 5 microns to 150 microns, or even 10 to 50 microns, preferably 2 to 50 microns, or even 15 to 50 microns.

[0186] For the purposes of the present invention, isocyanates useful in the present invention are understood to be isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be included in the term "isocyanate" as used herein.

[0187] Isocyanate is an aliphatic or aromatic monomer, oligomer or prepolymer, which can be used with two or more isocyanate functional groups. Isocyanate can be selected from aromatic toluene diisocyanate and derivatives thereof (for wall formation of encapsulates), or aliphatic monomers, oligomers or prepolymers, such as hexamethylene diisocyanate and dimer or trimer thereof, or 3,3,5-trimethyl-5-isocyanatomethyl-1-isocyanatocyclohexane tetramethylene diisocyanate. Polyisocyanates can be selected from 1,3-diisocyanato-2-methylbenzene, hydrogenated MDI, bis(4-isocyanatocyclohexyl)methane, dicyclohexylmethane-4,4'-diisocyanate and their oligomers and prepolymers. This list is illustrative and is not intended to limit the polyisocyanates available in the present invention.

[0188] Isocyanates useful in the present invention include isocyanate monomers, oligomers or prepolymers having at least two isocyanate groups, or dimers or trimers thereof. Optimized crosslinking can be achieved with isocyanates having at least three functional groups.

[0189] For the purposes of the present invention, isocyanates are understood to include any isocyanate monomer, oligomer, prepolymer or polymer having at least two isocyanate groups and containing aliphatic or aromatic moieties in the monomer, oligomer or prepolymer. If aromatic, the aromatic moiety may contain phenyl, toluyl, xylyl, naphthyl or diphenyl moieties, more preferably toluyl or xylyl moieties. For the purposes of the present invention, aromatic polyisocyanates may include diisocyanate derivatives such as biuret and polyisocyanurate. When aromatic, the polyisocyanate may be, but is not limited to, methylene diphenyl isocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, polyisocyanurates of toluene diisocyanate (known under the trade name RC is commercially available from Bayer), trimethylolpropane adduct of toluene diisocyanate (available under the trade name L75 is commercially available from Bayer) or trimethylolpropane adduct of xylylene diisocyanate (available under the trade name D-110N is commercially available from Mitsui Chemicals), naphthalene-1,5-diisocyanate, and phenylene diisocyanate.

[0190] Aliphatic isocyanates are understood to be monomeric, oligomeric, prepolymeric or polymeric polyisocyanates which do not contain any aromatic moieties. Aromatic polyisocyanates are preferred, however, aliphatic polyisocyanates and blends thereof are useful. Aliphatic polyisocyanates include trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (available from Mitsui Chemicals) or biuret of hexamethylene diisocyanate (available under the trade name N 100 is commercially available from Bayer).

[0191] The capsule shell may also be strengthened using additional co-crosslinkers such as multifunctional amines and / or polyamines, for example diethylenetriamine (DETA), polyethyleneimine and polyethyleneamine.

[0192] core

[0193] The microcapsules of the present invention include beneficial agents, which include one or more compositions intended to be encapsulated. Beneficial agents are selected from many different materials, such as chromogens and dyes, flavoring agents, spices, sweeteners, aromatics, oils, fats, pigments, cleaning oils, medicines, medicinal oils, perfume oils, mold inhibitors, antimicrobial agents, fungicides, bactericides, disinfectants, adhesives, phase change materials, odorants, fertilizers, nutrients and herbicides: as an illustration and not as a limitation. Beneficial agent and oil constitute the core. The core can be liquid or solid. For a core that is solid at ambient temperature, the wall material can be usefully wrapped with less than the entire core for some applications, such as the availability of the agglomerate core in an application is desirable. Such purposes can include odor release, cleaning compositions, emollients, cosmetic delivery, etc. When the microcapsule core is a phase change material, uses may include such encapsulated materials in mattresses, pillows, bedding, textiles, athletic equipment, medical devices, building products, construction products, HVAC, renewable energy, apparel, athletic surfaces, electronics, automotive, aviation, footwear, beauty care, laundry, and solar energy.

[0194] Useful benefit agents include fragrance raw materials such as alcohols, ketones, aldehydes, esters, ethers, nitriles, olefins, fragrances, fragrance solubilizers, essential oils, phase change materials, lubricants, colorants, coolants, preservatives, antimicrobial or antifungal actives, herbicides, antiviral actives, preservative actives, antioxidants, biologically actives, deodorants, emollients, humectants, exfoliants, UV absorbers, self-repairing compositions, corrosion inhibitors, sunscreens, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lipids, skin coolants, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching particles, silica particles, odor reducing agents, dyes, whitening agents, antibacterial actives, antiperspirant actives, cationic polymers, and mixtures thereof. By way of illustration and not limitation, phase change materials that can be used as beneficial agents may include paraffin hydrocarbons having 13-28 carbon atoms, various hydrocarbons such as n-octacosane, n-heptacosane, n-hexacosane, n-pentacosane, n-tetracosane, n-tricosane, n-docosane, n-heunesane, n-eicosane, n-nonadecane, octadecane, n-heptadecane, n-hexadecane, n-pentadecane, n-tetradecane, n-tridecane. The phase change material may alternatively optionally further include crystalline materials such as 2,2-dimethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, acids of linear or branched hydrocarbons such as eicosanoic acid and esters such as methyl palmitate, fatty alcohols, and mixtures thereof.

[0195] Preferably, in the case of fragrances, the fragrance oil acts as a solvent for the benefit agent and the wall forming material, as illustrated in the Examples herein.

[0196] Optionally, the aqueous phase may include an emulsifier. Non-limiting examples of emulsifiers include water-soluble salts of alkyl sulfates, alkyl ether sulfates, alkyl isothiosulfates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates, alkyl sulfates such as sodium lauryl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acyl aspartates, alkyl or alkyl ether or alkyl aryl ether phosphates, sodium lauryl sulfate, phospholipids or lecithin, or stearic acid soaps, sodium stearate, potassium stearate or ammonium stearate, oleate or palmitate, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, dialkyl sodium sulfosuccinate, dioctyl sodium sulfosuccinate, dilauryl sodium sulfosuccinate, poly(styrene sulfonate) sodium salt, isobutylene-maleic anhydride copolymer, gum arabic, sodium alginate, carboxymethyl cellulose, cellulose sulfate and pectin, poly(styrene sulfonate), isobutylene-maleic anhydride copolymer, carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gum and agar; semisynthetic polymers such as carboxymethyl cellulose, sulfated cellulose, sulfated methyl cellulose, carboxymethyl starch, phosphorylated starch, lignin sulfonic acid; and synthetic polymers such as maleic anhydride copolymers (including hydrolyzates thereof), polyacrylic acid, polymethacrylic acid, acrylic acid butyl acrylate copolymer or crotonic acid homopolymers and copolymers, vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers, and partial amides or partial esters of these polymers and copolymers, carboxyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphorylated or sulfated tristyrylphenol ethoxylates, palmitamidopropyltrimonium chloride (Varisoft PATC TM, available from Degussa Evonik, Essen, Germany), distearyl dimonium chloride, cetyl trimethyl ammonium chloride, quaternary ammonium compounds, fatty amines, aliphatic ammonium halides, alkyl dimethyl benzyl ammonium halides, alkyl dimethyl ethyl ammonium halides, polyethylene imine, poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary salt, poly(l-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), poly(acrylamide-co-diallyl dimethyl ammonium chloride), poly(allylamine), quaternized poly[bis(2-chloroethyl) ether-alt-1,3-bis[3-(dimethylamino)propyl] urea] and poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine), condensation products of aliphatic amines with alkylene oxides, quaternary ammonium compounds with long-chain aliphatic groups, for example distearyl diammonium chloride chloride), and fatty amines, alkyl dimethyl benzyl ammonium halides, alkyl dimethyl ethyl ammonium halides, polyalkylene glycol ethers, condensation products of alkyl phenols, aliphatic alcohols or fatty acids with alkylene oxides, ethoxylated alkyl phenols, ethoxylated aryl phenols, ethoxylated polyaryl phenols, carboxylic acid esters solubilized with polyols, polyvinyl alcohol, polyvinyl acetate, or copolymers of polyvinyl alcohol polyvinyl acetate, polyacrylamide, poly(N-isopropylacrylamide), poly(2-hydroxypropyl methacrylate), poly(-ethyl-2-oxazoline), poly(2-isopropenyl-2-oxazoline-co-methyl methacrylate), poly(methyl vinyl ether), and polyvinyl alcohol-co-ethylene), and cocamidopropyl betaine. Emulsifiers, if used, are typically present in an amount of about 0.1-40 weight percent, preferably 0.2 to about 15 weight percent, more typically 0.5 to 10 weight percent, based on the total weight of the formulation.

[0197] In addition to the benefit agent, the microcapsules may also encapsulate a partitioning modifier. Non-limiting examples of partitioning modifiers include isopropyl myristate, C4-C 24 Monoesters, diesters and triesters of fatty acids, castor oil, mineral oil, soybean oil, hexadecanoic acid, methyl ester isododecane, isoparaffin oil, polydimethylsiloxane, brominated vegetable oil and combinations thereof. The microcapsules can also have different proportions of distribution modifiers and benefit agents to prepare different microcapsule populations with different bloom patterns. These populations can also introduce different perfume oils to produce microcapsule populations showing different bloom patterns and different odor experiences. US2011-0268802 discloses other non-limiting examples of microcapsules and distribution modifiers and is incorporated herein by reference.

[0198] Optionally, if desired, the delivery particles can be dewatered, for example by decantation, filtration, centrifugation or other separation techniques. Alternatively, the aqueous slurry delivery particles can be spray dried.

[0199] In some examples of the method and composition, microcapsules may be composed of one or more different groups. The composition may have at least two different microcapsule groups, which differ in the exact composition of fragrance oil and median particle size and / or distribution modifier and fragrance oil (PM:PO) weight ratio. In some examples, the composition includes more than two different groups, which differ in the exact composition of fragrance oil and its breaking strength. In some other examples, microcapsule groups may differ in the weight ratio of distribution modifier and one or more fragrance oils. In some examples, the composition may include a first microcapsule group with a first ratio and a second microcapsule group with a second ratio, the first ratio being 2:3-3:2 for the weight ratio of distribution modifier and the first fragrance oil, and the second ratio being less than 2:3 but greater than 0 for the weight ratio of distribution modifier and the second fragrance oil.

[0200] In some embodiments, each different microcapsule population can be prepared in a different slurry. For example, a first microcapsule population can be contained in a first slurry and a second microcapsule population can be contained in a second slurry. It is understood that there is no limit to the number of different slurries used in combination, and the formulator's choice allows for the combination of 3, 10, or 15 different slurries. The first and second microcapsule populations can differ in the exact composition of the fragrance oil and in the median particle size and / or PM:PO weight ratio.

[0201] In some embodiments, the composition can be prepared by combining the first and second slurries with at least one auxiliary component, and optionally packaged in a container. In some instances, the first and second microcapsule groups can be prepared in different slurries, and then spray-dried to form particles. Different slurries can be mixed before spray drying, or spray-dried separately and then combined when in granular powder form. Once in powder form, the first and second microcapsule groups can be combined with auxiliary components to form a composition that can be used as a raw material for manufacturing consumer goods, industrial products, medical products or other commodities. In some instances, at least one microcapsule group is spray-dried and combined with the slurry of the second microcapsule group. In some instances, at least one microcapsule group is dried and prepared by spray drying, fluidized bed drying, tray drying or other available drying methods of this type.

[0202] In some examples, the slurry or dry particles may include one or more auxiliary materials, such as processing aids selected from the following substances: carriers, aggregation inhibiting materials, deposition aids, particle suspension polymers, and mixtures thereof. Non-limiting examples of aggregation inhibiting materials include salts that can have a charge shielding effect around the particles, such as magnesium chloride, calcium chloride, magnesium bromide, magnesium sulfate, and mixtures thereof. Non-limiting examples of particle suspension polymers include polymers such as xanthan gum, carrageenan, guar gum, shellac, alginates, chitosan; cellulosic materials such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, cationically charged cellulosic materials; polyacrylic acid; polyvinyl alcohol; hydrogenated castor oil; ethylene glycol distearate; and mixtures thereof.

[0203] In some embodiments, the slurry may include one or more processing aids selected from water, aggregation inhibiting materials such as divalent salts; particle suspending polymers such as xanthan gum, guar gum, carboxymethyl cellulose.

[0204] In other examples of the present invention, the slurry may include one or more carriers selected from polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, glycerin; non-polar solvents, including but not limited to mineral oil, fragrance raw materials, silicone oil, hydrocarbon paraffin oil, and mixtures thereof.

[0205] In some examples, the slurry may include a deposition aid, which may include a polymer selected from the group consisting of: polysaccharides, in one aspect, cationically modified starch and / or cationically modified guar gum; polysiloxanes; polydiallyldimethylammonium halides; copolymers of polydiallyldimethylammonium chloride and polyvinyl pyrrolidone; compositions comprising polyethylene glycol and polyvinyl pyrrolidone; acrylamide; imidazole; imidazolinium halides; polyvinylamine; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglyceryl ether silicone crosslinked polymers; copolymers of polyacrylic acid, polyacrylate, polyvinylamine and polyvinyl alcohol; oligomers of amines, in one aspect Diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine and mixtures thereof; polyethyleneimine, derivatized polyethyleneimine, in one aspect ethoxylated polyethyleneimine; polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties and nitrile moieties on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile or combinations thereof; preformed coacervates of anionic surfactants in combination with cationic polymers; polyamines and mixtures thereof.

[0206] In some additional examples used to illustrate the present invention, at least one microcapsule population may be contained in an agglomerate and then combined with a different microcapsule population and at least one auxiliary material. The agglomerate may include a material selected from the group consisting of silicon dioxide, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a binder such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0207] Suitable equipment for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, longitudinal axis granulators and drum mixers (both in batch and (when applicable) continuous process configurations), spray dryers and extruders. Such equipment can be obtained from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Kentucky, USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minnesota, USA), Arde Barinco (New Jersey, USA).

[0208] Test Method

[0209] Degradation % Determination Procedure

[0210] The % degradation is determined by the "OECD Chemical Testing Guide" 301B CO2 Release (Modified Sturm Test), adopted on July 17, 1992. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0211] Free oil measurement process

[0212] This method measures the amount of oil in the aqueous phase and uses 1 mg / ml dibutyl phthalate (DBP) / hexane as an internal standard solution.

[0213] Slightly more than 250 mg of DBP was weighed into a small beaker and transferred to a 250 ml container. Rinse the beaker thoroughly. Fill to 250 ml with hexane.

[0214] Sample preparation: About 1.5-2 grams (40 drops) of capsule slurry was weighed into a 20 ml scintillation vial and 10 ml of ISTD solution was added and the cap was tightly closed. After vigorous shaking several times within 30 minutes, the solution was pipetted into an autosampler vial and analyzed by GC.

[0215] Additional details. Instrument: HP5890 GC connected to HP Chem Station software; Column: 5m x 0.32 mm id with 1 μm DB-1 liquid phase; Temperature 50°C; hold for 1 minute then heat to 320°C; at 15 degrees / min; Injector: 275°C; Detector: 325°C; 2 ul injection.

[0216] Calculation: For both samples and calibration, add the total peak areas minus the area of ​​DBP.

[0217] i) Calculate mg of free core oil:

[0218]

[0219] ii) Calculate free core oil %

[0220]

[0221] Procedure for Beneficial Agent Leakage Determination

[0222] Obtain 2 one gram samples of the benefit agent granule composition. Add 1 gram (Sample 1) of the granule composition to 99 grams of the product base (where the granules will be used). Age the product base (Sample 1) containing the granules at 35°C in a sealed glass jar for 2 weeks. Similarly age another one gram sample (Sample 2).

[0223] After 2 weeks, filtration was used to recover particles of the granular composition from the product matrix (Sample 1) and from the granular composition (Sample 2). Each granular sample was treated with a solvent that would extract all of the beneficial agent from each sample particle. The solvent containing the beneficial agent from each sample was injected into a gas chromatograph and the peak areas were integrated to determine the total amount of beneficial agent extracted from each sample.

[0224] The beneficial agent leakage percentage is determined by calculating the difference obtained by subtracting the total amount of beneficial agent extracted from Sample 1 from the total amount of beneficial agent extracted from Sample 2, expressed as a percentage of the total amount of beneficial agent extracted from Sample 2, as shown in the following formula:

[0225]

[0226] Delivery particles can be prepared that exhibit a positive zeta potential. Such capsules have improved deposition efficiency, for example, on fabrics.

[0227] Sample preparation for biodegradability measurements

[0228] Water-soluble or water-dispersible materials were purified via crystallization until greater than 95% purity was achieved and dried prior to biodegradability measurements.

[0229] The oily medium containing the beneficial agent needs to be extracted from the delivery particle slurry in order to analyze only the polymer wall. Therefore, the delivery particle slurry is freeze-dried to obtain a powder. Then, it is further washed with an organic solvent via Soxhlet extraction to extract the oily medium containing the beneficial agent until the weight percentage of the oily medium based on the total delivery particle polymer wall is less than 5%. Finally, the polymer wall is dried and analyzed.

[0230] The weight ratio of delivery particles to solvent was 1:3. The residual oily medium was determined by thermogravimetric analysis (isothermal at 100°C for 60 minutes and at 250°C for another 60 minutes). The measured weight loss needed to be less than 5%.

[0231] OECD 301 B – Biodegradability Method

[0232] Within 60 days in accordance with the guidelines of the Organisation for Economic Cooperation and Development (OECD) - OECD (1992), Test No. 301: Ready Biodegradability, OECD Guidelines for the Testing of Chemicals, Part 3, OECD Publishing, Paris, https: / / doi.org / 10.1787 / 9789264070349-en To measure the cumulative CO2 release.

[0233] leakage

[0234] The amount of beneficial agent leakage from the beneficial agent-containing delivery particles was determined according to the following method:

[0235] i) Two 1 g samples of the stock slurry of delivery particles containing the benefit agent were obtained.

[0236] ii) 1 g of the raw slurry of delivery particles containing the benefit agent was added to 99 g of the consumer product base (where the particles were to be used) and the mixture was labeled Sample 1. A second 1 g sample of the raw particle slurry was used immediately in step d below in its pure form without contact with the consumer product base and was labeled Sample 2.

[0237] iii) The product matrix containing the delivery particles (Sample 1) was aged at 35°C in a sealed glass jar for 1 week.

[0238] iv) Particles were recovered from both samples using filtration. Particles in sample 1 (in the consumer product matrix) were recovered after the aging step. Particles in sample 2 (pure feedstock slurry) were recovered while the aging step was initiated at sample 1.

[0239] v) treating the recovered particles with a solvent to extract the benefit agent material from the particles.

[0240] vi) analyzing via chromatography the solvent containing the beneficial agent extracted from each sample.

[0241] vii) The resulting benefit agent peak areas under the curves were integrated and the areas summed to determine the total amount of benefit agent extracted from each sample.

[0242] viii) The percentage of beneficial agent leakage is determined by calculating the difference obtained by subtracting the total amount of beneficial agent extracted from Sample 1 (S1) from the total amount of beneficial agent extracted from Sample 2 (S2), expressed as a percentage of the total amount of beneficial agent extracted from Sample 2 (S2), as shown in the following formula:

[0243]

[0244] Volume weighted mean particle size

[0245] Particle size is measured using a static light scattering device such as an Accusizer 780A (manufactured by ParticleSizing Systems, Santa Barbara, California). The instrument is calibrated from 0 to 300μ using Duke particle size standards. Samples for particle size evaluation are prepared by diluting about 1 g of the emulsion if the volume weighted average particle size of the emulsion is to be determined, or 1 g of the delivery particle slurry containing the benefit agent if the volume weighted average particle size of the finished particles is to be determined, in about 5 g of deionized water, and further diluting about 1 g of this solution in about 25 g of water.

[0246] Add approximately 1 g of the maximum diluted sample to the Accusizer and start the test using the auto-dilution feature. The Accusizer should read over 9200 counts / second. If the count is less than 9200, additional sample should be added. The Accusizer will dilute the test sample until 9200 counts / second and begin evaluation. After 2 minutes of testing, the Accusizer will display the results, including the volume weighted average size.

[0247] The breadth index can be calculated by determining the particle size that accounts for more than 95% of the cumulative particle volume (95% size), the particle size that accounts for more than 5% of the cumulative particle volume (5% size), and the median particle size (50% size - 50% of the particle volume is above this size and 50% of the particle volume is below this size). Breadth index = ((95% size) - (5% size) / 50% size).

[0248] All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

[0249] It should be understood that each maximum numerical limit given throughout this specification includes each lower numerical limit, as if such lower numerical limits are clearly written in this article. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as if such higher numerical limits are clearly written in this article. Each numerical range given throughout this specification will include each narrower numerical range that falls within such a wider numerical range, as if all such narrower numerical ranges are clearly written in this article.

[0250] In the following examples, the abbreviations correspond to the materials listed in Table 1.

[0251] Table 1

[0252]

[0253] Example

[0254] Example 1: In-situ ATEC

[0255] Table 2

[0256] Material Quantity(g) DL-N-Acetylhomocysteine ​​Thiolactone (AHCTL) 8.92 Dytek HMDA (70%HMDA) 4.65 SR415 21.99 water 188.19 Research Accord 43.53 Captex 355 43.53

[0257] 1. Water was placed in a jacketed steel reactor and mixed with a flat 4-pointed mill blade at 750 rpm and maintained at 10C.

[0258] 2. Sprinkle AHCTL into the water with continuous mixing.

[0259] 3. Add HMDA dropwise with continuous mixing. pH was 4.0 before amine addition (mixing stopped). Maximum pH was about 10.83.

[0260] 4. Allow the aqueous solution to mix for 1 hour. The aqueous pH was about 9.39 after 1 hour of reaction.

[0261] 5. Increase the mill blade speed to 2000 rpm; slowly add SR415 using a plastic pipette.

[0262] 6. Increase the mill blade speed to 2500 rpm and add the Research Accord / Captex core dropwise using a plastic pipette.

[0263] 7. Increase the grinding speed to 3500 rpm; maintain the temperature at 10°C.

[0264] 8. Mix the batch at 10°C for about 4 hours.

[0265] The resulting microcapsules had a size of 0.67 μ (volume-weighted median) and exhibited low free core (1.9%) and low LFE leakage (31%).

[0266] Example 2: Interface ATEC

[0267] Table 3

[0268] Material Quantity(g) DL-N-Acetylhomocysteine ​​Thiolactone (AHCTL) 8.92 Dytek HMDA (70%HMDA) 4.65 SR415 21.99 water 188.19 Research Accord 43.53 Captex 355 43.53

[0269] 1. Water was placed in a jacketed steel reactor and mixed with a flat 4-pointed mill blade at 750 rpm and maintained at 20C.

[0270] 2. Sprinkle AHCTL into the water with continuous mixing.

[0271] 3. Add HMDA dropwise with continuous mixing. pH was 4.94 before amine addition (mixing stopped). Maximum pH was about 10.40.

[0272] 4. Allow the aqueous solution to mix for 3 hours. The aqueous pH was about 8.83 after 3 hours of reaction.

[0273] 5. Combine Research Accord, Captex, and SR415 in a glass beaker and mix until the solution is clear.

[0274] 6. Mixing at 2000 rpm, add the core solution dropwise to the water phase via pipette. This addition takes about 30-35 minutes. A white emulsion is produced when the oil phase is added, but no thickening is seen during the addition. The temperature is maintained at 20°C and the mixing speed is increased to 3000 rpm after all the oil phase is added. The emulsion color is bright white, no thickening is seen and no large lumps are seen. Cover the batch and allow it to mix overnight at 3000 rpm.

[0275] 7. The batch was mixed at room temperature for approximately 17 hours.

[0276] The resulting microcapsules had a volume weighted median particle size of 5.35 μ, 2.4% free core, and 60% LFE leakage.

[0277] Example 3: ATEC / PU Polymer preparation, capsule batch preparation)

[0278] For this process, an ATEC polymer emulsifier / crosslinker is produced in a first polymer preparation step, after which the polymer is used in a microencapsulation process where the polymer acts as the sole emulsifier in the process and also crosslinks the polyurea wall material.

[0279] Polymer preparation

[0280] Table 4

[0281]

[0282] 1. Add water to a 250 g beaker and stir with a magnetic stir bar.

[0283] 2. Add and stir SR610 to dissolve.

[0284] 3. Next add and mix HCTL and then add and mix AHCTL. After HCTL / AHCTL addition, the solution pH is about 3.87.

[0285] 4. Add BHMT and mix with a magnetic stir bar. During the BHMT addition, the pH reached a maximum of about 10.35 and then began to drop. After 1 hour the pH dropped to about 7.99.

[0286] 5. Adjust the pH back to 9 using 30% ammonia (0.79 g).

[0287] 6. After 2 hours the pH dropped back to about 8.56 and was adjusted back to 9 again using 30% ammonia (0.42 g).

[0288] 7. Cover the solution and allow to stir at room temperature for about 24 hours.

[0289] The polymer pH after the reaction was about 8.26. The polymer pH was adjusted to 5.84 (target 5.84) with 1.85 g of HCL. The solution was slightly viscous, golden in color and became slightly foamy upon mixing.

[0290] Microcapsule batch preparation:

[0291] Table 5

[0292] Material Quantity(g) Aqueous polymer (prepared in previous step) 200 Oil phase: Captex 355 195.69 Mondur MR 3.74 Desmodur N3200 0.57

[0293] 1. Add the aqueous phase to the jacketed reactor 1 at 22°C with mixing at 1000 rpm (4-tip flat mill). The mixer was offset on the reactor side with the blades almost touching the side.

[0294] 2. Add the oil phase (previously prepared and mixed with a magnetic stir bar at room temperature) to the mixed water phase via a plastic pipette. Mixing was initially set at 2000 rpm and increased to 2500 rpm after approximately half of the cores were added.

[0295] 3. Grinding speed increased to 4000 rpm and maintained at 22C.

[0296] 4. After grinding, mix the emulsion with a 3" propeller at 400 rpm.

[0297] 5. Before starting the curing stage, the emulsion was brought to a pH of 6.00 using caustic soda.

[0298] 6. Heat the batch from 22C to 65C in 30 minutes and hold at 65C for 4 hours.

[0299] 7. Allow the batch to cool naturally back to room temperature.

[0300] 8. After grinding, the pH of the emulsion was 4.76, 0.73 g of caustic soda (Decom Part #902-167) was used to bring the emulsion back to pH 6.03 (target 6.00).

[0301] The final microcapsule size (volume weighted median) was 6.52μ, free core was 0.5% and LFE leakage was 33%.

[0302] Example 4: ATEC / acrylate / PU

[0303] This process uses both ATEC and standard free radical acrylate chemistry to form the polymeric emulsifier used in the polyurea microencapsulation process. The ATEC polymer contains residual acrylate functional groups, which serve as reactive sites for subsequent acrylate reactions. In addition to acting as an emulsifier, the polymeric emulsifier contains amine functional groups, which are used to crosslink the isocyanate wall material.

[0304] Polymer Preparation - ATEC Polymers:

[0305] Table 6

[0306]

[0307] 1. Add water to a 250 g beaker and stir with a magnetic stir bar.

[0308] 2. Add and stir SR344 to dissolve.

[0309] 3. Next add and mix AHCTL. After AHCTL addition, solution pH is about 3.99. Before EDA addition, add 30% ammonia to adjust pH to about 9 (add 0.08 g ammonia solution).

[0310] 4. Add and mix EDA last. Add EDA during mixing with magnetic stir bar. After EDA addition, pH was about 10.25. pH dropped back down to below 9s quickly, so 2.33g of 30% ammonia was added to about pH 10.

[0311] 5. Mix the solution at room temperature overnight.

[0312] The polymer solution was clear with only a few particles visible. The solution was foamy when stirred vigorously. The polymer pH was 9.50.

[0313] Free Radical Acrylation Reactions on ATEC Polymers:

[0314] The A-TEC solution prepared above was placed in a jacketed steel reactor at 40°C with a nitrogen blanket of 100 cc / min and mixed with a flat 4-point mill blade at 1000 rpm. Another aqueous solution was prepared in a beaker using the composition shown in Table 7 below.

[0315] Table 7

[0316] Material Quantity(g) Wako V-50 0.2 TBAEMA 3.84

[0317] The A-TEC polymer from the previous step was placed in a jacketed steel reactor at 40 C, with a nitrogen blanket of 100 cc / min, and mixed at 750 rpm (4-tip flat mill).

[0318] 1. Add V-50 and TBAEMA directly to the reactor, with TBEMA added dropwise while mixing maintained at 750 rpm.

[0319] 2. Heat the solution from 40°C to 75°C in 30 minutes, hold at 75°C for 8 hours and then cool back to 25°C.

[0320] Table 8

[0321] Material Quantity(g) Aqueous polymer (prepared in previous step) 200 Oil phase: Captex 355 200 Mondur MR 4.0

[0322] Microcapsule preparation

[0323] 1. Add the aqueous phase to the jacketed reactor 1 at 20°C with mixing at 1000 rpm (4-tip flat mill). The mixer is offset on the side of the reactor with the blades almost touching the side.

[0324] 2. Add the oil phase (previously prepared and mixed with a magnetic stir bar at room temperature) to the mixed water phase via a plastic pipette. Mixing was initially at 2000 rpm and increased to 2500 rpm after adding approximately half of the cores.

[0325] 3. Increase the grinding speed to 4000 rpm and maintain the emulsion at 20°C throughout.

[0326] 4. After grinding, mix the emulsion with a 3" propeller at 425 rpm.

[0327] 5. Heat the batch from 20°C to 50°C in 30 minutes and hold at 50°C for 8 hours.

[0328] 6. Allow the batch to cool naturally back to room temperature.

[0329] The final microcapsules had a volume weighted median particle size of 15.8μ and had less than 1% free cores.

[0330] Example 5: ATEC / acrylate

[0331] The polymer preparation was accomplished in the same manner as in Example 3 (above), but with 19.31 g of SR610 (10% excess acrylate). The resulting polymer emulsifier contained residual acrylate functionality that was able to further react with the acrylate microcapsule wall derived from the oil phase.

[0332] 200 g of polymeric surfactant was placed in a beaker and Wako V50 initiator (0.3 g) was added and dissolved in the aqueous phase under mixing (magnetic stir bar). The aqueous phase was heated to 50 C for about 30 minutes before use.

[0333] A 50 / 50 mixture of limonene and Captex 355 (100 g) was added to a steel jacketed reactor at 35°C. A nitrogen blanket was applied at 100 cc / min. A flat 4-pointed grinder blade was used to mix at 300 rpm. Vazo 67 (0.3 g) and Vazo 88 (0.3 g) were added and dissolved. The reactor was heated from 35°C to 70°C in 45 minutes, kept at 70°C for 45 hours and cooled to 50°C in 45 minutes. A second oil phase (15 g of 50 / 50 limonene / Captex and 10 g of Sartomer SR206) was added and mixing continued for 60 minutes at 50°C. Mixing was stopped, the preheated water phase was added, and grinding was started (3000 rpm for 60 minutes while the temperature was maintained at 50°C). The size can be adjusted by changing the grinding speed and time. After grinding was complete, the mill blades were replaced with a 3" propeller mixer running at 300 rpm. The batch was heated from 50C to 70C, held at 70C for 4 hours, heated from 70C to 95C, and held at 95C for 6 hours before naturally cooling back to room temperature. The microcapsules produced can be used in aroma, agricultural, and phase change applications.

[0334] The percentage degradation was measured according to the OECD Guidelines for the Testing of Chemicals, Test Method OECD 301 B. A copy is available at www.oecd-ilibrary.org.

[0335] Capsules according to the invention may have a core to wall ratio of even up to 95 wt % core to 1 wt % wall. In applications where enhanced degradability is desired, higher core to wall ratios may be used, for example 99 wt % core to 1 wt % wall, or even 99.5 wt % to 0.5 wt % or higher. With appropriate selection of the core to wall ratio, the shell of the composition according to the invention may be selected to achieve the following % degradation when tested according to test method OECD 301B: at least 40% degradation after 14 days, at least 50% degradation after at least 20 days, and at least 60% degradation after at least 28 days.

[0336] Unless otherwise indicated herein or clearly contradictory to the context, the use of the singular "a", "an" is intended to cover both the singular and the plural. The terms "comprising", "having", "including" and "containing" are interpreted as open terms. All references cited herein (including publications, patent applications and patents) are incorporated herein by reference. Any description of some embodiments as "preferred" embodiments and other records of embodiments, features or ranges as preferred or suggesting that these are preferred are not considered restrictive. The invention is considered to include embodiments that are currently considered less preferred and can be described as such herein. Unless otherwise indicated herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order. Any and all examples or exemplary language (e.g., "for example") provided herein are intended to illustrate the present invention, rather than to impose limitations on the scope of the invention. Any statements herein about the attributes or benefits of the present invention or preferred embodiments are not intended to be restrictive. The present invention includes all modifications and equivalents of the subject matter recorded herein as permitted by applicable law. In addition, unless otherwise indicated herein or clearly contradictory to the context, the present invention includes any combination of the above-mentioned elements with all possible variations thereof. The description herein of any reference or patent, even if identified as "prior art," is not intended to constitute an admission that such reference or patent is available as prior art to the present invention. Unclaimed language should not be construed as limiting the scope of the present invention. Any statement or suggestion herein that certain features constitute components of the claimed invention is not intended to be limiting unless reflected in the appended claims.

Claims

1. A delivery particle comprising a core material and a shell encapsulating the core material, wherein the core material comprises a beneficial agent, and Wherein the shell comprises a polymer comprising a reaction product: an amine-thiol-ene conjugate.

2. The delivery particle of claim 1, wherein the amine of the amine-thiol-ene conjugate is a mono- or di-alkyldiamine, or a mono- or di-alkyltriamine.

3. The delivery particle of claim 1, wherein the thiol of the amine-thiol-ene conjugate is a thiolactone.

4. The delivery particle of claim 3, wherein the thiol of the amine-thiol-ene conjugate is selected from homocysteine ​​thiolactone and acetylated homocysteine ​​thiolactone. 5 . The delivery particle of claim 1 , wherein the alkene of the amine-thiol-ene conjugate is an unsaturated compound selected from vinyl compounds and acrylates.

6. The delivery particle of claim 1, wherein the amine-thiol-ene conjugate is additionally a free radical cross-linking reaction product of the amine-thiol-ene conjugate with one or more of a multifunctional (meth)acrylate and an isocyanate.

7. The delivery particle of claim 6, wherein the amine-thiol-ene conjugate comprises at least 50 wt% of the polymer.

8. The delivery particle of claim 1, wherein the amine-thiol-ene conjugate is additionally a reaction product of the amine-thiol-ene conjugate and a multifunctional (meth)acrylate.

9. The delivery particle of claim 5, wherein the vinyl compound further comprises a functional group comprising an electron withdrawing group.

10. The delivery particle of claim 1, wherein the amine-thiol-ene conjugate further comprises a reaction product of the amine-thiol-ene conjugate cross-linked with an isocyanate.

11. The delivery particle of claim 10, wherein the reaction product of the amine-thiol-ene conjugate and isocyanate is further free radically crosslinked with a multifunctional (meth)acrylate.

12. The delivery particle of claim 1, wherein the amine-thiol-ene conjugate comprises an additional cross-linking reaction product with one or more of an isocyanate, a Michael adduct comprising a multifunctional (meth)acrylate, or one or more of an aza-Michael adduct comprising a multifunctional acrylate.

13. The delivery particle of claim 1, comprising a core material and a shell encapsulating the core material, wherein the core material comprises a beneficial agent, and wherein the shell comprises a polymer comprising the reaction product of: Amines, thiolactones, polyfunctional (meth)acrylates and polyfunctional isocyanates.

14. The delivery particle of claim 1, wherein the amine-thiol-ene conjugate is a reaction product of an alkylamine, a 4-, 5- or 6-membered thiolactone and a vinyl compound having an electron withdrawing group.

15. The delivery particle of claim 14, wherein the alkylamine is selected from 3-18 carbon alkyl moieties.

16. The delivery particle of claim 1, wherein the thiolactone is selected from homocysteine-γ-thiolactone, acetylhomocysteine ​​thiolactone, α-amino-γ-thiobutyrolactone, N-acetylhomocysteine ​​thiolactone, α-isocyanato-γ-thiolactone, or N-(2-alkylacetyl)homocysteine ​​thiolactone.

17. The delivery particle of claim 1, wherein the molar ratio of amine to thiol to olefin moieties in the conjugate is 0.75 / 1 / 1.25 to 1.25 / 1 / 0.75, preferably 0.85 / 1 / 1.15 to 1.15 / 1 / 0.85, more preferably 0.95 / 1 / 1.05 to 1.05 / 1 / 0.

95.

18. The delivery particle of claim 11, wherein the multifunctional (meth)acrylate is present in molar excess compared to the thiolactone and the amine and is selected from oil-soluble (meth)acrylates selected from difunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, pentafunctional (meth)acrylates, hexafunctional (meth)acrylates, heptafunctional (meth)acrylates, octafunctional (meth)acrylates and mixtures thereof.

19. The delivery particle of claim 1, wherein the multifunctional (meth)acrylate is selected from water-soluble or water-dispersible (meth)acrylates independently selected from 2-carboxyethyl acrylate, 2-carboxyethyl acrylate oligomers, 2-carboxypropyl acrylate, 4-acryloyloxyphenylacetic acid, carboxyoctyl acrylate, tripropylene glycol diacrylate, ethoxylated bisphenol diacrylate, dipropylene glycol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ditrimethylolpropane triacrylate, dimethoxyl alcohol di ... propylene glycol diacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth)acrylate, cyanoethyl acrylate, 2-hydroxypropyl acrylate, lauryl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl chloride acrylate, aminoalkyl acrylate, ethylaminoethyl (meth)acrylate, aminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, diethylamino (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, or a combination of the foregoing.

20. The delivery particle of claim 1, wherein the shell further comprises an isocyanate compound, the isocyanate compound being aliphatic or aromatic and selected from one or more of isocyanate monomers, oligomers or prepolymers, dimers or trimers, having at least two isocyanate groups.

21. The delivery particle of claim 1, wherein the benefit agent is a fragrance, preferably the fragrance comprises a fragrance raw material characterized by a logP of about 2.5 to about 4.

5.

22. The delivery particle of claim 1, wherein the core further comprises a partition modifier selected from the group consisting of isopropyl myristate, vegetable oils, modified vegetable oils, mono-, di- and triesters of C4-C24 fatty acids, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, preferably isopropyl myristate.

23. The delivery particle of claim 1, wherein the wall has a biodegradability of greater than 30% CO2, preferably greater than 40% CO2, more preferably greater than 50% CO2, even more preferably greater than 60% CO2 (maximum 95%) within 60 days following the OECD 301B test.

24. The delivery particle of claim 1, wherein the wall of the delivery particle further comprises a coating material, preferably wherein the coating material is selected from the group consisting of poly(meth)acrylates, poly(ethylene-maleic anhydride), polyamines, waxes, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone-vinyl acrylate, polyvinylpyrrolidone methacrylate, polyvinylpyrrolidone / vinyl acetate, polyvinyl acetal, polyvinyl butyral, polysiloxanes, poly(propylene maleic anhydride), maleic anhydride derivatives, copolymers of maleic anhydride derivatives, polyvinyl alcohol, styrene- Butadiene latex, gelatin, gum arabic, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, other modified cellulose, sodium alginate, chitosan, chitin, casein, pectin, modified starch, polyvinyl acetal, polyvinyl butyral, polyvinyl methyl ether / maleic anhydride, polyvinyl pyrrolidone and its copolymers, poly(vinyl pyrrolidone / methacrylamidopropyltrimethylammonium chloride), polyvinyl pyrrolidone / vinyl acetate, polyvinyl pyrrolidone / dimethylaminoethyl methacrylate, polyvinyl amine, polyvinyl formamide, polyallylamine, copolymers of polyvinyl amine, and mixtures thereof.

25. The delivery particle of any of the preceding claims, wherein the delivery particle has a leakage of less than about 50%, or at most about 50%, as determined by the Leakage Test described in the Test Methods section.

26. The delivery particle of claim 1, wherein the delivery particle has a volume weighted median particle size of 5 to 150 microns, or even 10 to 50 microns, or even 15 to 50 microns.

27. An article incorporating a delivery particle according to any one of the preceding claims.

28. The article of claim 27, wherein the article is selected from the group consisting of an agricultural formulation, a slurry encapsulating an agricultural active, a population of dried microcapsules encapsulating an agricultural active, an agricultural formulation encapsulating a pesticide, and an agricultural formulation for delivering a pre-emergent herbicide.

29. The article of claim 27, wherein the agricultural active is selected from the group consisting of agricultural herbicides, agricultural pheromones, agricultural pesticides, agricultural nutrients, insect control agents, and plant stimulants.

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