Encapsulated curatives for curable and non-curable compositions

Abstract

Encapsulated curatives are useful for curable compositions, such as polyurethanes, epoxies, and other reactive polymer systems, to achieve optimized curing profiles, performance, stability, and reliable properties. Controlled release of curatives upon exposure to external stimuli for improved polymerization, stability, and shelf life of the curable compositions with reduced toxicity and handling risks. Encapsulation of reactive chemistries refers to isolating reactive chemical species within a protective matrix or shell, typically to control their reactivity, improve stability, and facilitate their targeted release under specific conditions.

Description

ENCAPSULATED CURATIVES FOR CURABLE ANDNON-CURABLE COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application hereby claims the benefit of the provisional patent application of the same title, Serial No. 63 / 747,588, filed on January 21, 2025, the disclosure of which is herein incorporated by reference in its entirety.BACKGROUND

[0002] Encapsulated curatives offer notable advantages in formulating and applying curable compositions. They offer controlled release, enhanced stability, improved handling, and increased versatility. These benefits create high-performance materials with consistent and reliable properties. As a result, encapsulated curatives are essential in various industrial applications, contributing to better product quality, safety, and efficiency.

[0003] The demand for low-temperature curing in resin systems, such as acrylates, epoxies, and polyurethanes, has emerged from the need to reduce energy consumption, enhance process efficiency, and accommodate heat-sensitive substrates. However, this shift presents challenges related to the shelflife and storage stability of these resins. Encapsulation provides a solution by allowing for the controlled release of curatives, ensuring they activate only under specific conditions, such as elevated temperatures, mechanical stress, or particular environmental factors. This precise activation contributes to consistent curing and polymerization processes.

[0004] A notable characteristic of encapsulated curatives is their non-migratory nature. Designed to remain primarily stationary within the carrier material, these curatives prevent premature reactions, ensuring they are only released when needed.

[0005] Encapsulation also protects curatives from adverse environmental factors such as moisture, oxygen, and UV light, which can degrade the curative and diminish its effectiveness. This protection not only extends the shelflife of the curative but also preserves the integrity of the overall curable composition. Moreover, encapsulated curatives can be stored for extended periods without significant loss of activity,- 1 - 120903.00007014918-6656-1929.1making them more practical for industrial applications that require long-term storage and consistent performance.

[0006] Another advantage of encapsulation is the reduction of workers' exposure to potentially hazardous curatives, thereby enhancing safety during handling and processing. This is especially important for curatives that are toxic or have strong odors. Highly reactive systems are typically incompatible with resins and must be protected until they are ready to react. Therefore, utilizing a highly reactive catalyst in curing compositions, for example, using super acids or blocked super acids, becomes more feasible for low-temperature curing. Encapsulating these highly reactive curatives addresses concerns regarding shelflife and storage stability. Some low- temperature curing resins may even necessitate refrigeration to extend their shelf life since they can gradually react or gel over time, even at room temperature.

[0007] The encapsulation of curatives facilitates better cross-linking and polymerization, enhancing mechanical properties such as tensile strength, flexibility, and durability of the final product. Additionally, encapsulation enables the integration of various curatives within a single system, allowing for complex curing mechanisms that can enhance the performance and properties of the final product. This capability is particularly valuable in applications requiring specific mechanical, thermal, or chemical characteristics. Encapsulated curatives also optimize curing profiles, allowing for faster or more controlled curing processes that can improve the efficiency and quality of manufacturing operations. This precise activation promotes consistent curing and polymerization processes.BRIEF SUMMARY

[0008] Encapsulated curatives comprise of plurality of cores derived from organic and inorganic microporous and mesoporous particles, wherein the curative optionally resides within the particle or interstitial spaces between plurality of carrier material particles, or wherein the curative is bound to the plurality of carrier material particles on their surface or in between the particles through physical, mechanical, or associative forces.

[0009] In some embodiments, the encapsulated curative as recited above, wherein at least two particles of said plurality of particles that are not chemically bound.120903.000070\4918-6656-1929.1 - 2 -

[0010] In some embodiments, the encapsulated curative as recited above, wherein none of, some of, or all of the said plurality of carrier material particles have internal porosity.

[0011] In some embodiments, the encapsulated curatives as recited above, wherein the carrier material comprises at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, and an oligomer.

[0012] In some embodiments, the encapsulated curatives as recited above, wherein the inorganic metal compounds comprise silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, and combination thereof.

[0013] In some embodiments, the encapsulated curatives as recited above, wherein the inorganic metal oxide is silica.

[0014] In some embodiments, the encapsulated curatives as recited above, wherein the inorganic metal oxide is silica and alumina.

[0015] In some embodiments, the cores as recited above, wherein the silica is precipitated or fumed silica or quartz.

[0016] In some embodiments, the encapsulated curative as recited above, comprises of metal organic framework (MOF).

[0017] In some embodiments, the encapsulated curative comprises zeolites.

[0018] In some embodiments, the encapsulated curative as recited above, wherein the mesoporous carrier material is selected from thermoplastic urethane (TPU), polystyrene, polymethyl methacrylate (PMMA), polylactic acid (PLA), polyvinyl alcohol (PVA), polyether ether ketone (PEEK), polyethylenimine (PEI), nylon, polyester, polycarbonate, polyolefin, polyglycolic acid, polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polychlorotrifluoroethylene, phenol -formaldehyde (Bakelite), para-aramids (Kevlar and Twaron), polychloroprene (neoprene), natural rubber, meta-aramids (Nomex), PAN (Orlon), polybutadiene, styrene-butadiene, copolyamide (Technora), polyimide (Ultem), aromatic polyesters (Vectran), poly(vinyl poly-p-phenylene-2,6-benzobisoxazole idene fluoride-co-120903.000070\4918-6656-1929.1 - 3 -hexafluoropropylene) (Viton), poly-p-phenylene-2,6-benzobisoxazole (Zylon), and blends, mixtures, or alloys thereof.

[0019] In some embodiments, the encapsulated curatives as recited above, wherein the curative comprises Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2- ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.

[0020] In some embodiments, the encapsulated curatives; the curatives additionally comprise accelerators.

[0021] The encapsulated curatives are added to the curing agents in another embodiment. For example, in free radical polymerization, AIBN is a versatile initiator for free radical polymerization of acrylates. Its thermal decomposition generates radicals that efficiently initiate the polymerization of various acrylate monomers. The combination of copper ions and AIBN enables faster polymerization. Vitrification is a crucial phenomenon in the polymerization of acrylates that significantly impacts the curing process and final properties of the material. As vitrification progresses, the reaction becomes diffusion-controlled rather than chemically controlled, considerably slowing down the curing rate. Adding the encapsulated Cu accelerator to the composition containing acrylates and AIBN would allow controlled free radical polymerization. The release of Cu ion curatives steadily prevents resin verification, resulting in uniform polymerization and superior performance characteristics.

[0022] In some embodiments, the encapsulated curatives are used in curing formulations containing acrylates, isocyanate trimerization, polyurethanes, or epoxy chemistries.

[0023] In some embodiments, the encapsulated curatives as recited above, wherein the encapsulated curatives are devoid of the shell.120903.000070\4918-6656-1929.1 -4 -

[0024] In some embodiments, the encapsulated curatives as recited above, wherein the encapsulated curatives further comprise of core shell configurations; comprising at least one polymeric or oligomeric shell fully or partially covering the plurality of core material particles.

[0025] In some embodiments, the encapsulated curative is made by treating the sodium aluminum silicate (Sipernate 807, Evonik) with copper 2-Ethyl hexanoate, metal exchange results in the Cu+2 aluminum silicate.

[0026] In some embodiments, the encapsulated curative is made by treating silanated silica (Sipernate D10, Evonik).

[0027] An encapsulated curative composition, comprising a plurality of carrier particles, a curative, a shell, and a surfactant. The plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof. The curative: (i) resides within one or more of the carrier particles, (ii) resides within the interstitial spaces between the plurality of carrier particles, or (iii) is bound to a surface of one or more of the carrier particles. The shell encapsulates the carrier particles and the curative.

[0028] A curable resin comprising the encapsulated curative composition or a curative composition. The curative composition may be a non -encapsulated curative or an amalgamated curative. The encapsulated curative composition in the curable resin may be activated to initiate a chemical reaction to cure the curable resin.

[0029] A method of making an encapsulated curative. The method comprises the steps of: mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal aluminum silicate curative composition. The curative composition is mixed with a resin solution in water-soluble solvents. The curative composition and resin solution are mixed with an aqueous solution comprising a surfactant to disperse the curative composition particles in water. The resin is deposited onto the curative composition particle by solvent deposition to form the encapsulated curative.

[0030] A method of making an encapsulated curative. The method comprises the steps of: mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal aluminum silicate curative composition.120903.000070\4918-6656-1929.1 -5 -Mixing the curative composition with a resin solution in an organic solvent. Spray drying the mixture of the curative composition and resin solution to form an encapsulated curative.

[0031] A curative composition comprises a plurality of carrier particles and a curative. The plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof. The curative: (i) resides within one or more of the carrier particles, (ii) resides within the interstitial spaces between the plurality of carrier particles, or (iii) is bound to a surface of one or more of the carrier particles. In some embodiments, the curative additionally comprises a matrix that holds the carrier particles together.

[0032] A method of making a curative composition comprises mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth.

[0033] These and other objects and advantages shall be made apparent from the accompanying drawings and the description thereof.BRIEF DESCRIPTION OF THE FIGURES

[0034] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the general description given above, and the detailed description of the embodiments given below, serve to explain the principles of the present disclosure.

[0035] FIG. l is a schematic of an embodiment of an encapsulated curative and shows heat activation.

[0036] FIG. 2 is a schematic of amalgamated curative

[0037] FIG. 3 is a schematic of core-shell particles.

[0038] FIG. 4 is a schematic of how the curatives can be characterized.

[0039] FIG. 5 is an FTIR spectra of samples from Example 9.

[0040] FIG. 6 is an FTIR spectra of samples from Example 10.

[0041] FIG. 7 is an NMR spectra of the surfactant (PVOH) extracted from the shell of the encapsulated curatives from Example 10.120903.000070\4918-6656-1929.1 - 6 -

[0042] FIG. 8 is a differential scanning calorimetry thermogram from Example 12.DETAILED DESCRIPTION

[0043] The encapsulated curatives disclosed in this disclosure can exist in core-shell and core-only configurations. In contrast to the core-only configuration with no shell, the core-shell configuration has a protective shell around the core.

[0044] The core-only configuration functions to deliver curatives, including accelerators, into the curable formulations. For instance, metals such as copper or other transition elements in their different oxidation states are commonly used as curatives. The core-only configuration allows the transfer of ions into a curing composition using cores.

[0045] The metals are bound into the cores through ionic, van der Waals, coordinate covalent bonds. Thermal, mechanical, pH, shock, or other physical and chemical triggers facilitate the release of the metals for the carrier.

[0046] In cases where encapsulated curatives have a core-shell configuration, the shell protects the curatives and enables controlled release. For example, in copper - catalyzed radical polymerization, high concentrations of copper can lead to rapid reaction kinetics, forming a seed with polymerized material encrusting the copper surface. This encrustation renders the copper unavailable for the reaction. The shell's chemistry can be designed to deform gradually in response to temperature, pressure, pH, viscosity, and other factors. By controlling the formation of the shell, we can achieve a controlled release of the encapsulated curative, leading to controlled and uniform polymerization. Shell materials derived from thermoplastic polymers allow for gradual deformation beyond the glass transition temperature of the shell. By carefully managing the shell's chemistry, it is possible to release the payload instantaneously or over an extended period. This capability is particularly valuable for reactions that require the availability of the curative throughout the reaction.

[0047] Several triggers can initiate the release of encapsulated curatives that are not limited to mechanical pressure or shear forces that rupture the shell, changes in pH that degrade the core or dissolve the core, temperature increases that melt or soften the core, exposure to specific solvents that dissolve the walls of the shell or the core.120903.000070\4918-6656-1929.1 - 7 -

[0048] Encapsulated curatives can be used in various industries, particularly for enhancing the performance, stability, and application of curable compositions such as polyurethanes, epoxies, and other polymer systems. Encapsulated curatives can be used in various industries related to adhesives, binders, coatings, inks, and sealants.

[0049] In some embodiments, inorganic and organic cores are used as carriers for curatives.

[0050] Surprisingly, the curatives used in this context can be incorporated into the cores disclosed in PCT Patent Application No. PCT / US2024 / 025251 to Malofsky et al. (the “PCT filing”), which is fully incorporated into this document, as if that patent reference were set forth fully, here. Also fully incorporated by reference into this document are PCT Patent Application Nos. PCT / US2025 / 052486 and PCT / US2025 / 059035, as if they were set forth fully, herein.

[0051] Encapsulated curatives are useful for curable compositions, such as polyurethanes, epoxies, and other reactive polymer systems, to achieve optimized curing profiles, performance, stability, and reliable properties. Controlled release of curatives upon exposure to external stimuli for improved polymerization, stability, and shelflife of the curable compositions with reduced toxicity and handling risks. Encapsulation of reactive chemistries refers to isolating reactive chemical species within a protective matrix or shell, typically to control their reactivity, improve stability, and facilitate their targeted release under specific conditions.

[0052] Encapsulated curatives may be described as a core and shell curative. The curative is made up of discrete particles. The particles have a shell that encapsulates the core. The shell acts as a barrier to prevent the release of the core, which contains the curative and the carrier particles. The latency from curing is primarily due to the shell acting as a barrier. Multiple different shells and cores may be used with an encapsulated curative.

[0053] Non-encapsulated curatives may be amalgamated or non-amalgamated curatives. Amalgamated curatives are made up of particles. They are an amalgamation of carrier particles, curative, and a matrix. The matrix binds the carrier particles and curative together and does not comprise a discrete shell. In some embodiments, the amalgamated curative particles are a homogeneous mixture of120903.000070\4918-6656-1929.1 - 8 -carrier particles, curative, and polymer. Non-amalgamated curatives comprise carrier particles and curative. The curative may reside within the carrier particles, the interstitial spaces between the carrier particles, or bound to the surface of the carrier particles.

[0054] Encapsulated curative

[0055] An encapsulated curative comprises a plurality of carrier particles, a curative, a shell, and a surfactant. The plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof. The curative (i) resides within one or more of the carrier particles, (ii) resides within the interstitial spaces between the plurality of carrier particles, or (iii) is bound to a surface of one or more of the carrier particles. The shell encapsulates the carrier particles and the curative. An encapsulated curating is a core-shell curative. There are discrete particles that form the core which comprise the curative. The shell acts as a barrier for releasing the curative. The latency of curing is primarily provided by the shell.

[0056] In some embodiments, the carrier particles are not chemically bound together.In some embodiments, the carrier particles have internal porosity. In some embodiments, the carrier particles comprise mesoporous or microporous silica particles. In some embodiments, the carrier particles have an average particle size of 1 - 1,000 microns; such as from about 1 to about 10, about 10 to about 20, about 20 to about 30, about 30 to about 40, about 40 to about 50, about 50 to about 60, about 60 to about 70, about 70 to about 80, about 80 to about 90, about 90 to about 100, about 100 to about 200, about 200 to about 300, about 300 to about 400, about 400 to about 500, about 500 to about 600, about 600 to about 700, about 700 to about 800, about 800 to about 900, about 900 to about 100 microns.

[0057] In some embodiments, the encapsulated particles have a D5 particle size of 1 - 1,000 microns; such as from about 1 to about 10, about 10 to about 20, about 20 to about 30, about 30 to about 40, about 40 to about 50, about 50 to about 60, about 60 to about 70, about 70 to about 80, about 80 to about 90, about 90 to about 100, about 100 to about 200, about 200 to about 300, about 300 to about 400, about 400 to about 500, about 500 to about 600, about 600 to about 700, about 700 to about 800, about 800 to about 900, about 900 to about 100 microns.120903.000070\4918-6656-1929.1 - 9 -

[0058] In some embodiments, the carrier particles comprise at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof. Examples of an inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof. In some embodiments, the inorganic metal salt comprises aluminum silicate with alkali or alkali earth metal counter ions. In some embodiments, the inorganic metal salt comprises silicates of transition or inner transition elements. In some embodiments, the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof. In some embodiments, the carrier particles comprise silica. In some embodiments, the carrier particles comprise silica and alumina. In some embodiments, the silica is precipitated or fumed silica or quartz. In some embodiments, the carrier particles comprise zeolites.

[0059] In some embodiments, the encapsulated curative composition comprises a metal organic framework (MOF).

[0060] In some embodiments the carrier particles are mesoporous. Examples of the carrier particles include thermoplastic urethane (TPU), polystyrene, polymethyl methacrylate (PMMA), polylactic acid (PLA), polyvinyl alcohol (PVA), polyether ether ketone (PEEK), polyethylenimine (PEI), nylon, polyester, polycarbonate, polyolefin, polyglycolic acid, polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polychlorotrifluoroethylene, phenol -formaldehyde (Bakelite), para-aramids (Kevlar and Twaron), polychloroprene (neoprene), natural rubber, meta-aramids (Nomex), PAN (Orlon), polybutadiene, styrene-butadiene, copolyamide (Technora), polyimide (Ultem), aromatic polyesters (Vectran), poly(vinyl poly-p-phenylene-2,6- benzobisoxazole idene fluoride-co-hexafluoropropylene) (Viton), poly-p-phenylene- 2,6-benzobisoxazole (Zylon), and blends, mixtures, or alloys thereof. In some embodiments, the carrier particles are PMMA, polyurethane, or combinations thereof.

[0061] In some embodiments, the curative comprises Cu(II) carboxylates, Cu(II) chelates, metal alkoxides, bismuth carboxylates, zinc carboxylates, tin carboxylates, amine catalysts, heterocyclic amines, quaternary ammonium catalysts,120903.000070\4918-6656-1929.1 - 10 -dicyandiamides, diureas, diamines, blocked sulfonic acids, or combinations thereof. In some embodiments, the curative comprises metal carboxylates with ligands, wherein the ligands are selected from ethylenediamine (en); 2,2' -bipyridine (bipy); 1,10-phenanthroline (phen); oxalate (C2O42, oxalato), acetyl acetonate (acac ); diethylenetriamine (dien); EDTA (ethylenediaminetetraacetate); or combinations thereof. In some embodiments, the ligands are carboxylates. In some embodiments, the ligands are 2-ethylhexanoate, octoanoate, or combinations thereof. In some embodiments, the metal carboxylate and ligands are bound to the carrier through hydrogen bonds.

[0062] In some embodiments, the accelerators or co-accelerators comprises Cu(II) carboxylates, Cu(II) chelates, metal alkoxides, bismuth carboxylates, zinc carboxylates, tin carboxylates, amine catalysts, heterocyclic amines, quaternary ammonium catalysts, dicyandiamides, diureas, diamines, blocked sulfonic acids, or combinations thereof. In some embodiments, the curative comprises metal carboxylates with ligands, wherein the ligands are selected from ethylenediamine (en); 2,2'-bipyridine (bipy); 1,10-phenanthroline (phen); oxalate (C2O42, oxalato), acetyl acetonate (acac ); diethylenetriamine (dien); EDTA (ethylenediaminetetraacetate); or combinations thereof. In some embodiments, the ligands are carboxylates. In some embodiments, the ligands are 2-ethylhexanoate, octoanoate, or combinations thereof. In some embodiments, the metal carboxylate and ligands are bound to the carrier through hydrogen bonds.

[0063] In some embodiments, the curative comprises Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof. In some embodiments, the curative comprises Cu(II) 2-ethyl hexanoate, K-Kat XK-651 (bismuth), or combinations thereof.120903.000070\4918-6656-1929.1 - 11 -

[0064] In some embodiments, the accelerators or co-accelerators comprises Cu(II) 2- ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K- Kat XK-651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof. In some embodiments, the accelerators or co-accelerators comprises Cu(II) 2-ethyl hexanoate, K-Kat XK-651 (bismuth), or combinations thereof.

[0065] The curative (curing agent) is the chemically active component that reacts to form crosslinked polymers, while the carrier is believed to be a (largely) inert phase that transports, dilutes, protects, or controls the release of that curative until the desired cure event.

[0066] In some embodiments, the encapsulated curative composition further comprises accelerators. In some embodiments, the accelerators or co-accelerators comprises Cu(II) 2-ethyl hexanoate, K-Kat XK-651, DBTDL (dibutyltin dilaurate), K-Kat XK-682 (bismuth), imidazole, substituted imidazole, and combinations thereof.

[0067] In some embodiments, the shell is formed from monomers of epoxy and thermoplastic polymers comprising polyester, polyurethane, or combinations thereof. Example monomers include epoxy monomers selected from Epon 1001, Epon 1004, Epon 1007, or a combination thereof. In some embodiments, the shell is formed from styrenic polymers and copolymers, polamides, polyimides, polyethylene (PE: LDPE, LLDPE, HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS, including HIPS, EPS), polyethylene terephthalate (PET, PETG), polyamide / Nylon (PA6, PA66, others), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), PC / ABS blends, and combinations thereof.

[0068] In some embodiments, the shell comprises a non-porous shell region and a porous shell region. In some embodiments, the shell surrounds a portion of the core. In some embodiments, the shell surrounds the entire core. In some embodiments, it is believed that during the formation of the shell, solvent gets trapped in the shell. As the encapsulated curative is dried, the solvents escape leaving pores in the shell.120903.000070\4918-6656-1929.1 - 12 -

[0069] In some embodiments, the surfactant is selected from ionic surfactants and non-ionic surfactants. Example surfactants include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxy cholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof. In some embodiments, the surfactant is PVP, such as K-grade homopolymers selected from K-17, K-30, K-60, K-90, or combinations thereof. In some embodiments, the surfactant has a modified polyvinyl alcohol (PVA) backbone, which may be optionally partially hydrolyzed, wherein the backbone carries additional functional groups to impart tailored surface activity and compatibility. The functional groups may include carboxyl groups, which provide anionic character and enhance dispersibility in aqueous systems, or cationic moieties, which confer positive charge for improved adhesion to negatively charged substrates. Examples of modified PVA includes the Kuraray POVAL® K series. In some embodiments, the surfactant is present in an amount of from 1-20% by weight. In some embodiments, the surfactant is present in an amount of from 1-5, 5-10, 10-15, or 15-20 % by weight.

[0070] In some embodiments, the surfactant is on or in the shell. The shell may be about 10% w / w of the encapsulated curative particles.

[0071] In some embodiments, the encapsulated curative further comprises susceptors.These susceptors assist the release of the curative from the encapsulation. Examples of susceptors include microwave susceptors, Rf susceptors, or both. In some embodiments, the susceptor is selected from fullerene compounds, graphene, graphite oxide, nanocrystalline cellulose single- single-walled carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more ferrous metals, oxides of one or more ferrous metals. SPIONS, one or more non-ferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, or more combinations thereof.

[0072] Curable Resin

[0073] A curable resin composition comprises an encapsulated curative composition and a thermosetting resin. In some embodiments, the thermosetting resin comprises120903.000070\4918-6656-1929.1 - 13 -acrylates, silane-terminated polymers, isocyanates, polyurethane, polyurea, epoxy, amino crosslinking resins, or combinations thereof. In some embodiments, the thermosetting resin comprises epoxy, acrylates, or polyurethanes. In some embodiments, the melt temperature of the thermosetting resin is within 20 °C of the latency temperature of the shell. The latency temperature is the temperature at which the curative is released from the encapsulation. In some embodiments, the thermosetting resin of the curable resin composition is the same thermosetting resin of the shell of the encapsulated curative. By having the shell of the encapsulated curative be similar or the same as the thermosetting resin, after activation of the curative by rupturing of the shell, the shell material can be incorporated into the thermoset resin without materially altering the thermoset resin’s properties.

[0074] The viscosity of the curable resin affects its handling properties when used in molds or when 3D printed. In some embodiments, the curable resin composition exhibits a viscosity of 500 to 30,000 mPa s (cps) at 23°C, as measured by ASTM D 7867. This range of viscosity enables the curable resin to be used in applications for casting, coating, dispensing or printing while providing for adequate suspension of fillers and encapsulated curatives. In some embodiments, the curable resin has a viscosity of 500 to 30,000 mPas, such as 500 to 750, 750 to 1,000, 1,000 to 2,000, 2,000 to 3,000, 3,000 to 4,000, 4,000 to 5,000, 5,000 to 7,500, 7,500 to 10,000, 10,000 to 12,000, 12,000 to 14,000, 14,000 to 16,000, 16,000 to 18,000, 18,000 to 20,000, 20,000 to 22,000, 22,000 to 24,000, 24,000 to 26,000, 26,000 to 28,000, or 28,000 to 30,000 mPa s.

[0075] In some embodiments, the curable resin composition exhibits a viscosity of 500 to 30,000 mPa s (cps) at 23°C. This may balance the low-flow sag resistance with good wet-out of substrates and reinforcement fibers in composite, adhesive, and encapsulant applications.

[0076] In some embodiments, the curable resin composition exhibits a viscosity of 3,500 mPa s (cps) or less at 40°C. For example between 500 and 3,500 mPa s (cps) or less at 40°C. This may facilitate additive manufacturing or thin-film coatings, and allow high-resolution printing.

[0077] In some embodiments, the curable resin composition is stable while still containing the encapsulated curative. This allows the curable resin composition to be120903.000070\4918-6656-1929.1 - 14 -handled, stored, modified, and transported without curing. In some embodiments, the curable resin composition is storage stable at 25°C for at least 3 months, such as at least 6 months, as at least 12 months, or at least 24 months. Storage stable means that the viscosity drift is less than 20%, there is no gelation, and the resin does not physically separate. In some embodiments, the curable resin composition is substantially uncured after exposure to 40°C for 7 days. Substantially uncured means that less than 10% of the reactive groups of the resin composition have been cured, as determined by spectroscopy of DSC. In some embodiments, the curable resin composition is storage stable after exposure to 40°C for 7 days. In some embodiments, the curable resin composition is storage stable after thermal cycling between -20°C and 50°C three times.

[0078] Curing the resin

[0079] The curable resin may be cured by initiating a chemical reaction, this is done by activating the encapsulated curative, which means releasing the curative from the encapsulation. The chemical reaction may be initiated by the curative in the encapsulated curative. For liquid thermosets, encapsulated curatives (including accelerators or co-accelerators) can be dispersed into a low-viscosity resin or diluent to make a masterbatch, which is later let down into the final formulation to minimize handling and breakage of the shell. Stirred into epoxy or other liquid resins using mechanical stirring, (propeller, anchor, planetary) at low to moderate rpm, chosen so the capsules distribute uniformly without excessive rupture. In some embodiments, the encapsulated curatives, accelerators, or co-accelerators are blended into liquid thermoset resins using FlackTek mixing, which refers to a bladeless, high-speed dual asymmetric centrifugal (DAC) mixing process performed in closed containers using FlackTek-brand mixers. Other DAC mixers include Hauschild SpeedMixer and Resodyn Acoustic Mixers.

[0080] In some embodiments, the activation step comprises a thermal step selected from oven heating, infrared heating, induction heating, contact heating, and combinations thereof. In some embodiments, the activation step comprises treatment with UV light, IR light, or a combination thereof. In some embodiments, the activation step comprises heating the composition to a temperature of about 50 °C to about 200 °C. In some embodiments, the activation step comprises maintaining the120903.000070\4918-6656-1929.1 - 15 -temperature of the composition at a temperature for a period of about 1 to 1,000 minutes. In some embodiments, the activation step comprises impinging the bulk reaction mixture with at least one frequency of RF radiation and / or at least one frequency of MW radiation. In some embodiments, the impinging of at least one frequency of RF radiation and / or at least one frequency of MW radiation is performed periodically, wherein the period is regular or irregular. In some embodiments, the activation step comprises impinging the bulk reaction mixture with electromagnetic radiation frequencies ranging from about 50 MHz to about 30 GHz. In some embodiments, the electromagnetic radiation frequency ranges from about 915 MHz to about 2.45 GHz. In some embodiments, the electromagnetic radiation has a power in the range of about 1 W to about 10,000 W. In some embodiments, the electromagnetic radiation is impinged for about 10 seconds to about 60 minutes.

[0081] In some embodiments, the curable resin composition may contain two different curatives which enable dual curing. For example, the first curative may be activated by one mechanism, such as a light induced activation or low temperature cure. A second curative may be activated later by a similar or different mechanism, such as RF or MW radiation, heat, or water exposure. This second curing step may allow for a more complete curing process, such as after the partially cured resin is removed from a mold. The curable resin composition may comprise a nonencapsulated, an agglomerated, an encapsulated curative, or any combination thereof.

[0082] The chemical reaction cures the curable resin. Examples of the chemical reaction are polymerization.

[0083] In some embodiments, the curable resin composition exhibits a snap-cure profile in which gelation occurs within 1-20 minutes after activation at 80-180°C. For example, the curable resin composition may be cured within 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 12 minutes, 14 minutes, 15 minutes, 17 minutes, 18 minutes, or 20 minutes. In some embodiments, the curable resin composition is fully cured (>90% conversion) within 30 minutes or less, such as within 25 minutes, 20 minutes, 15 minutes, 10 minutes, or 5 minutes. This snap-cure profile allows fast cycle times in composite molding, electronics, adhesive assembly, 3D printing, and others.120903.00007014918-6656-1929.1 - 16 -

[0084] Method of making an encapsulated curative

[0085] The encapsulated curative may be made by mixing the carrier particles with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal -carrier composition. The metal-carrier composition is mixed with a resin solution in a water- soluble solvent and a surfactant. The resin is deposited onto the curative composition particle by solvent deposition to form the encapsulated curative.

[0086] The resin is deposited onto the curative composition particle to form the encapsulated curative. In some embodiments, the resin is deposited onto the curative composition to form the encapsulated curative by fluidizing the curative composition in a fluid bed coater to form fluidized particles. A uniform film or layered coating is formed on the fluidized particles by spraying a resin solution onto the fluidized particles. In some embodiments, the resin solution is sprayed upwards onto the fluidized particles. In some embodiments, the resin solution is sprayed downwards onto the fluidized particles. In some embodiments, resin is deposited onto the curative composition to form the encapsulated curative by removing the aqueous solution. In some embodiments, the resin is deposited onto the curative composition particle to form the encapsulated curative by spray drying.

[0087] In some embodiments, the shell is formed by a solvent-deposition process in which a resin-containing solution is brought into contact with the curative composition particle, and the solvent is then removed. During this solvent-removal step, the resin not only deposits at the particle-fluid interface but also undergoes partial polymerization and / or crosslinking, so that the deposited layer transitions from a solvated resin film into a more solid, partially cured polymer shell. It is believed that shell formation is driven by a combination of physical deposition (from solvent evaporation or extraction) and chemical reaction within the resin, which improves shell cohesion, mechanical integrity, and resistance to premature rupture while still allowing subsequent full cure under the desired activation conditions.

[0088] In some embodiments, the resin comprises a polymer or polymer precursor dissolved or dispersed in a solvent. In some embodiments, the solvent is water. In some embodiments, the solvent is an organic solvent. Examples of organic solvent include dichloromethane, THF, methyl ethyl ketone, and acetone.120903.000070\4918-6656-1929.1 - 17 -

[0089] In some embodiments, in a solvent deposition process, the solvent is soluble in water.

[0090] In some embodiments, the resin solution comprises an epoxy resin, an acrylate resin, a polyurethane prepolymer, a benzoxazine, a cyanate ester, or combinations thereof. Examples of the epoxy resin include EPON 100 IF, 1004F, 1007F, or combinations thereof. In some embodiments, the shell is formed from styrenic polymers and copolymers, polamides, polyimides, polyethylene (PE: LDPE, LLDPE, HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS, including HIPS, EPS), polyethylene terephthalate (PET, PETG), polyamide / Nylon (PA6, PA66, others), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), styreneacrylonitrile (SAN), PC / ABS blends, and combinations thereof.

[0091] In some embodiments, the carrier particles are sodium aluminum silicate. In some embodiments, the metal salts or metal ligands of copper, iron, tin, or bismuth is copper 2-ethyl hexanoate. After mixing with the sodium aluminum silicate, a Cu(II) aluminum silicate is formed.

[0092] In some embodiments, the carrier particles comprise at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof. Examples of an inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof. In some embodiments, the inorganic metal salt comprises aluminum silicate with alkali or alkali earth metal counter ions. In some embodiments, the inorganic metal salt comprises silicates of transition or inner transition elements. In some embodiments, the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof. In some embodiments, the carrier particles comprise silica. In some embodiments, the carrier particles comprise silica and alumina. In some embodiments, the silica is precipitated or fumed silica or quartz. In some embodiments, the carrier particles comprise zeolites.120903.000070\4918-6656-1929.1 - 18 -

[0093] In some embodiments, a susceptor is added to the mixture prior to removal of the aqueous solution. In some embodiments, the susceptor is dispersed or dissolved into the resin solution; when the shell is formed the susceptor is in the shell.

[0094] In some embodiments, the sodium aluminum silicate comprises micro or mesoporosity suitable for the adsorption of metal carboxylates. In some embodiments, the copper 2-ethylhexanoate is present in an amount effective to form Cu(II) surface complexes immobilized on the aluminosilicate surface.

[0095] In some embodiments, the surfactant is selected from anionic, cationic, nonionic, or amphoteric. It is present at a concentration sufficient to maintain a stable aqueous dispersion during the addition and solvent removal.

[0096] In some embodiments, the solvent is removed by atmospheric evaporation under stirring. In some embodiments, the solvent is removed by mild heating and / or reduced pressure to deposit a continuous or semi -continuous resin shell.

[0097] Non-encapsulated curative

[0098] In some embodiments, the accelerators or co-accelerators comprises Cu(II) 2- ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K- Kat XK-651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof. In some embodiments, the accelerators or co-accelerators comprises Cu(II) 2-ethyl hexanoate, K-Kat XK-651 (bismuth), or combinations thereof.

[0099] In some embodiments, the curative composition does not include a shell and / or a surfactant. In some embodiments, a curative composition comprises a plurality of carrier particles and a curative. The plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof. The curative: (i) resides within one or more of the carrier particles, (ii) resides within the interstitial spaces between the plurality of carrier particles, or (iii) is bound to a surface of one or more of the carrier particles.120903.000070\4918-6656-1929.1 - 19 -

[0100] In some embodiments, the carrier particles are not chemically bound together. In some embodiments, the carrier particles have internal porosity. In some embodiments, the carrier particles comprise mesoporous or microporous silica particles. In some embodiments, the carrier particles have an average particle size of 1 - 1,000 microns; such as from about 1 to about 10, about 10 to about 20, about 20 to about 30, about 30 to about 40, about 40 to about 50, about 50 to about 60, about 60 to about 70, about 70 to about 80, about 80 to about 90, about 90 to about 100, about 100 to about 200, about 200 to about 300, about 300 to about 400, about 400 to about 500, about 500 to about 600, about 600 to about 700, about 700 to about 800, about 800 to about 900, about 900 to about 100 microns.

[0101] In some embodiments, the carrier particles comprise at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof. Examples of an inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof. In some embodiments, the inorganic metal salt comprises aluminum silicate with alkali or alkali earth metal counter ions. In some embodiments, the inorganic metal salt comprises silicates of transition or inner transition elements. In some embodiments, the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof. In some embodiments, the carrier particles comprise silica. In some embodiments, the carrier particles comprise silica and alumina. In some embodiments, the silica is precipitated or fumed silica or quartz. In some embodiments, the carrier particles comprise zeolites.

[0102] In some embodiments, the curative comprises Cu(II) carboxylates, Cu(II) chelates, metal alkoxides, bismuth carboxylates, zinc carboxylates, tin carboxylates, amine catalysts, heterocyclic amines, quaternary ammonium catalysts, dicyandiamides, diureas, diamines, blocked sulfonic acids, or combinations thereof. In some embodiments, the curative comprises metal carboxylates with ligands, wherein the ligands are selected from ethylenediamine (en); 2,2' -bipyridine (bipy); 1,10-phenanthroline (phen); oxalate (C2O42, oxalato), acetyl acetonate (acac ); diethylenetriamine (dien); EDTA (ethylenediaminetetraacetate); or combinations120903.000070\4918-6656-1929.1 - 20 -thereof. In some embodiments, the metal carboxylate and ligands are bound to the carrier through hydrogen bonds.

[0103] In some embodiments, the curative comprises Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.

[0104] Method of Making a non-encapsulated curative composition

[0105] The curative composition may be made by mixing the carrier particles with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal -carrier composition.

[0106] In some embodiments, the carrier particles are sodium aluminum silicate. In some embodiments, the metal salts or metal ligands of copper, iron, tin, or bismuth is copper 2-ethyl hexanoate. After mixing with the sodium aluminum silicate, a Cu(II) aluminum silicate is formed.

[0107] In some embodiments, the carrier particles comprise at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof. Examples of an inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof. In some embodiments, the inorganic metal salt comprises aluminum silicate with alkali or alkali earth metal counter ions. In some embodiments, the inorganic metal salt comprises silicates of transition or inner transition elements. In some embodiments, the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof. In some embodiments, the carrier particles comprise silica. In some embodiments, the carrier particles comprise silica and alumina. In some embodiments, the silica is precipitated120903.000070\4918-6656-1929.1 - 21 -or fumed silica or quartz. In some embodiments, the carrier particles comprise zeolites.

[0108] In some embodiments, the curative composition is formed by mixing a sodium aluminum silicate with Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2- ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.

[0109] The curative composition may be formed into particles by spray coating, solvent deposition with agitation, or ultrasonication.

[0110] In some embodiments, the curative composition, further comprises a matrix that holds the carrier particles together. This is an amalgamated curative, which is made up of particles. They are an amalgamation of carrier particles, curative, and a matrix. The matrix binds the carrier particles and curative together and does not comprise a discrete shell. In some embodiments, the amalgamated curative particles are a homogeneous mixture of carrier particles, curative, and matrix.

[0111] In some embodiments, the matrix is a polymer. For example, the matrix is formed from monomers of epoxy and thermoplastic polymers comprising polyester, polyurethane, or combinations thereof. Examples include a matrix formed from epoxy monomers selected from Epon 1001, Epon 1004, Epon 1007, or a combination thereof. In some embodiments, the matrix is formed from styrenic polymers and copolymers, polamides, polyimides, polyethylene (PE: LDPE, LLDPE, HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS, including HIPS, EPS), polyethylene terephthalate (PET, PETG), polyamide / Nylon (PA6, PA66, others), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), styreneacrylonitrile (SAN), PC / ABS blends, and combinations thereof.

[0112] In some embodiments, the curative composition further comprises a surfactant. Examples of the surfactant include sodium dodecyl sulfate, sodium120903.000070\4918-6656-1929.1 - 22 -dodecylbenzene sulfonate, sodium cholate, sodium deoxy cholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof.

[0113] In some embodiments, after loading the curative into the carrier, the polarity of the resulting core material is altered relative to the native carrier surface, and the core is subsequently subjected to organophilization to restore compatibility with the shell -forming medium.

[0114] Organophilization is the process of converting an inorganic, typically hydrophilic mineral surface into a more organophilic surface by introducing organic groups, usually through ion exchange or covalent grafting.

[0115] In some embodiments, organophilization is achieved by salination or other post-functionalization of surface hydroxyl or other reactive groups on the core, for example by treatment with one or more organosilane coupling agents and / or grafting of organic polymers or oligomers.

[0116] In some embodiments, the organosilane comprises a hydrophilic or polar functionality (e.g., epoxy, amino, or hydroxyl) capable of reacting or interacting with the core surface and a hydrophobic or otherwise compatibility -tuned organic group selected to match the polarity and surface energy of the shell -forming resin, monomer, or prepolymer.

[0117] In some embodiments, the core is first functionalized with initiator or chain-transfer groups and then subjected to a surface-initiated polymerization (“grafting-from”) or reaction with pre-formed polymers (“grafting-to”) to provide a polymeric moiety whose chemical nature is tailored to the chemistry used to form the shell.

[0118] In some embodiments, the resulting post-functionalized core exhibits improved wetting by the shell-forming phase, reduced interfacial tension, and enhanced interfacial adhesion between the core and shell, thereby promoting the formation of uniform, defect-free core-shell microcapsules or particles.120903.000070\4918-6656-1929.1 - 23 -

[0119] In some embodiments, such surface-modified cores also display improved dispersion stability in the shell-forming medium and in any downstream matrix into which the core-shell particles are incorporated.

[0120] In some embodiments, the step of organophilization comprises treatment of the core with 3 -Aminopropyltri ethoxy silane (APTES),3 -Aminopropyltrimethoxy silane, N-(2-Aminoethyl)-3 -aminopropyltrimethoxy silane, Epoxy / glycidoxy silanes (epoxy, urethane, acrylic systems; fillers pretreatment), 3 -Glycidoxypropyltrimethoxy silane (GPTMS, GLYMO),3-Glycidoxypropyltriethoxysilane, tetraethyl orthosilicate (TEOS),2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, Methacryloxy / acryloxy silanes (unsaturated polyester, acrylics, optical fibers),3 -Methacryloxypropyltrimethoxy silane (MEMO),3 -Methacryloxypropyltri ethoxy silane, Mercapto silanes,3 -Mercaptopropyltrimethoxy silane, 3 -Mercaptopropyltri ethoxy silane,(3 -Mercaptopropyl)methyldimethoxy silane, 3 -Isocyanatopropyltri ethoxy silane, or a combination thereof.

[0121] In some embodiments, the step of organophilization comprises treatment of the core with propyltriethoxysilane, tetraethyl orthosilicate (TEOS), or combinations thereof.

[0122] In some embodiments, the loading of the organosilane is 0.5-3 mmol of functional groups per gram of carrier. In some embodiments, the core comprises about 5-25 wt% organic content on the core.

[0123] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

[0124] Except where expressly noted, trademarks are shown in upper case.

[0125] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.120903.000070\4918-6656-1929.1 - 24 -

[0126] Unless stated otherwise, pressures expressed in psi units would be gauge, and pressures expressed in kPa units would be absolute. Pressure differences, however, are expressed as absolute (for example, pressure 1 is 25 psi higher than pressure 2).

[0127] When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range.

[0128] When the term “about” is used, it is used to mean a certain effect or result can be obtained within a certain tolerance, and the skilled person knows how to obtain the tolerance. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.

[0129] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0130] The transitional phrase "consisting of' excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of' appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0131] The transitional phrase "consisting essentially of' limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. A “consisting essentially of’ claim120903.000070\4918-6656-1929.1 - 25 -occupies a middle ground between closed claims that are written in a “consisting of’ format and fully open claims that are drafted in a “comprising” format. Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term “consisting essentially of.”

[0132] Further, unless expressly stated to the contrary, "or" and “and / or” refers to an inclusive and not to an exclusive. For example, a condition A or B, or A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0133] The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0134] It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or excluded, each individual embodiment is deemed to be combinable with any other embodiment s) and such a combination is considered to be another embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as "solely," "only" and the like in connection with the recitation of claim elements, or use of a "negative" limitation. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself.

[0135] While the present disclosure has illustrated by description several embodiments and while the illustrative embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications may readily appear to those skilled in the art. Furthermore, features120903.000070\4918-6656-1929.1 - 26 -from separate lists can be combined; and features from the examples can be generalized to the whole disclosure.

[0136] All references cited in this document are incorporated by reference as if fully set forth herein.

[0137] Encapsulated curatives comprise a plurality of cores derived from organic and inorganic microporous and mesoporous particles, wherein the curative optionally resides within the particle or interstitial spaces between plurality of carrier material particles, or wherein curative is bound to the plurality of carrier material particles on their surface or in between the particles through physical, mechanical, or associative forces.

[0138] In some embodiments, the core, or the core shell particle as recited in the PCT filing comprises the releasable ingredient without the susceptor particle. The releasable ingredient is the encapsulated curative as defined herein. The curative is released by mechanisms described herein and not necessarily through radio frequency or microwave as described in the PCT filing.

[0139] The encapsulated curatives have applications for the following: fiber composites; particulate composites; reinforced by polymer composites, laminar, flex or rigid, composites; adhesively bound articles, temporary or permanent; coated articles; fibers; coated fibers; patterned printed in two- or three-dimension materials; and porosity and foam sealing.EXAMPLES

[0140] NCR samples are curative compositions and can be identified by their names.For example, NCR-EMI50 is a curative composition with 50 wt% loading of the EMI 24 catalyst, which is 2-ethyl-4-methylimidazole, produced by Evonik. NCR-EMI25- E1F4 is a curative composition referred to the coating of Epon 1001F (shell) on NCR- EMI25 (core) in 1 :4 wt ratio respectively. NCR-EMI25 refers to the particles with 25wt% loading of the EMI24 catalyst; “E1F” refers to Epon epoxy 1001F; “4” refers to 4 parts of Epon epoxy to 1 part EMI catalyst.120903.000070\4918-6656-1929.1 - 27 -Example 1: Procedure for making encapsulated curatives with core-only configuration (RR-807- Cu)

[0141] Take 150 g Sipernate 807 in an Erlenmeyer flask. Take a 2 wt.% Copper(II) 2- ethylhexanoate of the amount of 807 taken (which would be 0.75 g of Copper(II) 2- ethylhexanoate in this case.) Add 800 mL ethanol to the Copper(II) 2-ethylhexanoate (Copper 2 EHA). Slowly add the copper solution to the Erlenmeyer flask with silica. Put it for stirring using a mechanical stirrer for 12 hours. Sonicate for an additional 30 minutes. Centrifuged the materials and isolated the encapsulated Cu as a precipitate. The precipitate was dried at 50 C to obtain a colorless white powder (RR- 807- Cu)

[0142] Formulations:Control Acrylate mixture + AIBN (control)Reference : Acrylate mixture + AIBN + Copper 2 EHAExperiment: Acrylate mixture + AIBN + RR-807-Cu

[0143] Formulations of 2 gm each (control, reference, and experiment) were applied on the surface of the wood (2 -inch square) and heated to 120 C for 30 minutes.

[0144] Observations: Comparing the curing of different formulations on a wooden block, we observed:- The reference and the experiment samples cured faster than the control.- The experiment sample had a smooth and uniform surface compared to the reference.- The reference sample had a flaky appearance.Example 2: Procedure for making encapsulated curatives with core-shell configuration

[0145] To enable the coating with lipophilic core chemistry, the hydrophilic RR-807- Cu is silanated.

[0146] Silane Modification (RR-807- Silane): Prepare a 20% silane solution in 150 ml ethanol. Add the silane solution to the wet particles of (RR-807- Cu) while stirring. Prepare 10 ml of DI water in a separate vial and adjust pH to 8-9 using NH40H. Add the pH-adjusted water to the particle mixture. Add 150 ml more ethanol to the system. Heat the mixture to 60°C and stir for at least 8 hours. Allow particles to precipitate. Filter the RR-807- Silane particles120903.000070\4918-6656-1929.1 - 28 -

[0147] Coating a shell around silane particles (RR-807-Shell): The silane-modified ( RR-807-Silane) is coated with a shell comprising PMMA and Epon 1007F. Measure 100 g of the RR-807- Silane particles. Add 60 g of resin solution (1007F, 0.1 g / ml in THF) to the particles. Add 20 g of PMMA solution (0.1 g / ml) while stirring at 60°C. Add THF to bring the total volume to 300 ml. Stir the mixture for at least 4 hours. In a separate container, prepare 600 ml of 1% PVA solution. Slowly add the particle / resin / PMMA mixture to the PVA solution using a pump, while stirring at room temperature. Continue stirring for at least 6 hours. Collect the final product in bottles for filtration.

[0148] Formulations:Control Acrylate mixture + AIBN (control)Reference : Acrylate mixture + AIBN + Copper 2 EHAExperiment: Acrylate mixture + AIBN + (RR-807-Shell)

[0149] Formulations 2 gm each (control, reference, and experiment) were applied on the surface of the wood (2 -inch square) and heated to 120 C for 30 minutes.

[0150] Observations: Comparing the curing of different formulations on a wooden block, we observed:- The reference and the experiment samples cured faster than the control.- The experiment sample had a smooth and uniform surface compared to the reference.- The reference sample had a flaky appearance.Example 3: Procedure for making NCR-EMI 10 (core-only configuration)

[0151] 10.0 g of EMI24 (2-ethyl-4-methylimidazole) was dissolved in 350 ml ethanol and stirred for 15 minutes at 300 RPM till the imidazole completely dissolves. 90.0 g of Sipernat 807 was added to this solution and stirred for additional 12 to 16 hrs. The solvent was allowed to evaporate at 60°C and the dry powder was dried further in the oven at 55° for 12 to 16 hours.Example 4: Procedure for making NCR-EMI 10-E1F4 (encapsulated curative)

[0152] Weigh 40.0 g of EPON 1001F add to 375 - 500 mL THF and stirred the mixture at rt at 300 rpm till you get a homogeneous solution. Weigh 8.33 g of NCR- EMI 10 and add to the solution. Add 2 mL DCM to the epoxy -NCR mixture in the120903.000070\4918-6656-1929.1 - 29 -first RBF. Stir the mixture for at least 24 hours. In a second round bottom flask (500 mL), add 700 mL of 1% PVOH in DI water solution and a magnetic stir bar. Stir the second RBF at 400 rpm. A peristaltic pump was used to facilitate the transfer of the epoxy mixture containing NCR-EMI10 into the 1- 10% PVOH solution at the rate of 1.8- 18 mL per second while the mixture was being stirred at 400 rpm. Once all epoxy mixture was transferred into the 1% PVOH solution, the mixture was stirred for 16 hours or overnight at rt. The mixture was stirred at least 1200 rpm for 6 hours. The settled particles were dried using a vacuum oven rt . The dried particles were sieved using a 60 mesh size and the final particles were collected.Example 5: Procedure for making NCR-EMI10-E IF 1 amalgamated curatives using spray dry process

[0153] Weigh 40.0 g of EPON 100 IF add to 375 mL THF and stirred the mixture at rt at 300 rpm till you get a homogeneous solution. Weigh 8.33 g of NCR-EMI10 and add it to the Epon 1001F solution. Under constant mixing, the mixture of NCR- EMI10 and Epoxy 100 IF in THF was sprayed into a spray dryer, equipped with the two-fluid spray gun through 1.2 mm atomizing nozzle. The inlet temperature of 110- 125 C and spray atomization of 10- 20 PSI.Example 6: Stability Study

[0154] 9.8 g of Epon 824 and 0.2 g of catalytic additive were weighed and mixed in the FlackTek for 10 minutes @ 2500 RPM. 8.0 g of this mixture was transferred to an aluminum pan and put in an oven set at 100°C. The status of curing was checked every 5 minutes using a metal spatula.Curative Curing durationEMI24 30 minutesNCR-EMH0 30 minutesNCR-EMH0-E1F4 45 minutes

[0155] This shows that the various curatives protected the resin from curing compared with a catalyst.Example 7: Shelf-life Study

[0156] The shelf-life of the curatives were studies and compared to a catalyst. 7.21 g of Epon 824 and 2.40 g of DDSA was weighed and mixed in a FlackTek for 10120903.000070\4918-6656-1929.1 -30 -minutes @ 2500 RPM. 0.19 g of catalytic additive was added to this mixture and mixed in the FlackTek for 10 minutes @ 2500 RPM. 8.0 g of this mixture was transferred to a 9-dram glass vial and put in an oven set at 55°C. The cure status of the samples was checked every 24 hours for 7 days.Curative Curing durationControl (No additive) Gel formation in 2 daysEMI24 Cured in 24 hours NCR-EMI10 Gel formation in 2 days NCR-EMI10-E1F4 Flowy, stable, no curing for 7 daysExample 8: Viscosity Study

[0157] Viscosity was measured over time. For the control, 22.06 g of Epon 828 and 7.35 g of DDSA was weighed and mixed in a FlackTek for 10 minutes @ 2500 RPM. For the rest of the samples, 21.63 g of Epon 828 and 7.21 g of DDSA was weighed and mixed in a FlackTek for 10 minutes at 2500 rpm. 0.59 g of catalytic additive was added to this mixture using FlackTek at 2500 rpm for 5 minutes. Spindle 3 was used for the viscometer measurements. The spindle was lowered into the sample till the spindle immersion mark was reached. The speed of the spindle was set, and the experiment was allowed to occur for 300 seconds. The speed of the spindle was adjusted so as to keep the F.S.% close to 50 (+ / - 5%). And the final accurate reading was noted. This data is referred to as Day 0. The formulation was allowed to sit for 24 hours. The formulation was mixed in the Flacktek at 2500 rpm for 30 seconds and the viscosity was measured again (Day 1). This process was repeated for 2 more days.Day 0:Viscosity Temperature Additive Spindle Speed (mPas.) F.S.% (°C)Control (No additive) 3 13.0 4948.5 53.6 23.6 EMI24 3 2.0 30100.4 50.1 24.2 NCR-EMI10 3 8.0 7744.1 51.6 24.3 NCR-EMI10-E1F4 3 12.0 5173.1 51.7 24.0Viscosity TemperatureAdditive S Control (No additive) 3 5825.324.3EMI24120903.000070\4918-6656-1929.1 - 31 -NCR-EMI10 3 5.0 11514.5 47.9 24.2 NCR-EMI10-E1F4 3 13.0 5995.0 49.9 24.0Day 2:Viscosity Temperature Additive Spindle Speed (mPas.) F.S.% (°C) Control (No additive) 3 9.0 4948.5 49.8 24.1EMI24 3 - - - - NCR-EMI10 3 3.0 20567.6 51.4 24.0NCR-EMI10-E1F4 3 12.0 6911.4 51.8 23.8Day 3:Viscosity Temperature Additive Spindle Speed (mPas.) F.S.% (°C) Control (No additive) 3 8.0 7978.8 53.1 23.9EMI24 3 - - - - NCR-EMI10 3 - - - - NCR-EMI10-E1F4 3 7.0 8431.3 52.6 24.1Example 9: Characterization o f Curative Shell

[0158] A schematic of how the curatives can be characterized is shown in FIG. 4.

[0159] Curative NCR-EMI10-E1F4 was characterized by FTIR spectroscopy.

[0160] FTIR spectroscopy helps us to confirm the identity of the epoxy coating for the encapsulated NCR particles. By analyzing the infrared spectra, overlapping peaks indicate similarities in functional groups. The fingerprint region (1500-500 cm-1) is especially specific, making even minor differences between samples apparent. Since the technique is fast, non-destructive, and requires minimal sample preparation, it is ideal for analyzing limited material while enabling repeated measurements for accurate comparison.

[0161] A background spectrum was collected with a clean ATR crystal. The curative sample (NCR-EMI10-E1F4) sample was placed directly onto the ATR crystal. Gentle pressure was applied using the ATR pressure arm to ensure good contact between the solid surface and the crystal. FTIR spectra were recorded in the range of 4000-400 cm1with 32 scans.

[0162] The FTIR spectra are shown in FIG. 5.120903.000070\4918-6656-1929.1 - 32 -characterizationNo. Wavenumber Chemical group Symmetrical & asymmetrical C-H stretch in 1 3030 cm’1aromatics.2 2960 cm’1Asymmetrical C-H stretch of-CH? group.3 2920 cm’1Asymmetrical C-H stretch of-CH2 group.4 2860 cm’1Symmetrical C-H stretch of-CH? group 1604.48 cm’1, 1583.27 cm’1,5 1502.27 cm’1and 1463.70.09 cm’1C-C stretching vibration in aromatic 6 1292.07 cm -CH2 deformation7 1232.27 cm’1Asymmetrical aromatic C-0 stretch. 8 1178.29 cm’1Asymmetrical aliphatic C-0 stretch. 9 1027.87 cm’1Symmetrical aromatic C-0 stretch 958.44 cm’1, 912.16 cm’1and10 862.03 cm’1Epoxide ring vibrations11 827.31 cm’1-CH out of plane deformation in aromatic.Example 10: Extraction and Characterization o f Curative

[0163] The carrier material was extracted from a curative and characterized.

[0164] 4.0 g of NCR-EMI10-E1F4 was taken and added to 250 ml of DI water. This mixture was refluxed at 100°C for 4 hours. The mixture was allowed to cool. After centrifuging the mixture and collecting the supernatant, the supernatant was filtered using a Q8 filter paper. This supernatant was transferred to a beaker and the water was allowed to evaporate by keeping the beaker on a hot plate set at 70°C. The final solid was scraped off and collected in a glass vial, which was characterized by FTIR and NMR. See FIGs. 6 and 7.Spectra characterizationNo. Wavenumber Chemical groupO-H from the intermolecular and1 3200-3500 cm'1intramolecular hydrogen bonds 2 2870-2900 cm’1C-H from alkyl groups 3 1140 cm'1C-0 (crystallinity) 4 1050-1085 cm’1C-O-CExample 11: Density measurements

[0165] The density of the various curatives was measured using a pycnometer.120903.00007014918-6656-1929.1 - 33 -Experiment Sample Name Specific Gravity1 Sipernat 807 2.052 NCR-EMI50 1.383 NCR-EMI25 1.294 NCR-EMI25-E1F4 0.655 NCR-EMI10 1.786 NCR-EMI10-E1F4 0.857 NCR-Cu 1.97Example 12: Differential Scanning Calorimetry

[0166] The DSC curve shows the onset temperature of the control EMI -24 and NCR- EMI50 in an epoxy resin and anhydride formulation. Samples were cured with a ramp rate of 10°C / min and isothermal at 165°C for 30 minutes. The DSC thermogram is shown in FIG. 8.Example 13: Laser Diffraction Graph

[0167] Particle size distribution was measured via laser diffraction.Experiment Sample Name D10 D50 D90 Span1 NCR-EMI25 1.49 8.39 23.77 2.662 NCR-EMI10-E1F4 4.68 35.81 111.67 2.993 NCR-EMI25-E1F4 5.11 21.93 119.95 5.24120903.000070\4918-6656-1929.1 - 34 -

Claims

1. CLAIMSEncapsulated curative1. An encapsulated curative composition, comprising a plurality of carrier particles, a curative, a shell, and a surfactantwherein the plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof, wherein the curative:(i) resides within one or more of the carrier particles,(ii) resides within the interstitial spaces between the plurality of carrier particles, or(iii) is bound to a surface of one or more of the carrier particles, wherein the shell encapsulates the carrier particles and the curative.

2. The encapsulated curative composition of claim 1, wherein the shell comprises a non- porous shell region and a porous shell region.

3. The encapsulated curative composition of claim 1, wherein the carrier particles are not chemically bound.

4. The encapsulated curative composition of any one of claims 1-3, wherein the carrier particles have internal porosity.

5. The encapsulated curative composition of any one of claims 1-4, wherein the carrier particles comprise mesoporous or microporous silica particles.

6. The encapsulated curative composition of any one of claims 1-5, wherein the carrier particles have an average particle size of 1 - 1,000 microns.

7. The encapsulated curative composition of any one of claims 1-6, wherein the carrier particles comprises at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof.120903.000070\4918-6656-1929.1 - 35 -8. The encapsulated curative composition of claim 7, wherein the inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof.

9. The encapsulated curative composition of claim 7, wherein the inorganic metal salt comprises aluminum silicate with alkali or alkali earth metal counter ions.

10. The encapsulated curative composition of claim 7, wherein the inorganic metal salt comprises silicates of transition or inner transition elements.

11. The encapsulated curative composition of any one of claims 1-10, wherein the carrier particles comprises an inorganic metal salt, wherein the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof.

12. The encapsulated curative composition of any one of claims 1-11, wherein the carrier particles comprise silica.

13. The encapsulated curative composition of any one of claims 1-12, wherein the carrier particles comprise silica and alumina.

14. The encapsulated curative composition of any one of claims 11-13, wherein the silica is precipitated or fumed silica or quartz.

15. The encapsulated curative composition of any one of claims 1-14, further comprising a metal organic framework (MOF).

16. The encapsulated curative composition of any one of claims 1-15, wherein the carrier particles comprise zeolites.120903.000070\4918-6656-1929.1 - 36 -17. The encapsulated curative composition of any one of claims 1-16, wherein the carrier particles are mesoporous, wherein the carrier particles are selected from thermoplastic urethane (TPU), polystyrene, polymethyl methacrylate (PMMA), polylactic acid (PLA), polyvinyl alcohol (PVA), polyether ether ketone (PEEK), polyethylenimine (PEI), nylon, polyester, polycarbonate, polyolefin, polyglycolic acid, polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polychlorotrifluoroethylene, phenol-formaldehyde (Bakelite), para-aramids (Kevlar and Twaron), polychloroprene (neoprene), natural rubber, meta-aramids (Nomex), PAN (Orlon), polybutadiene, styrene-butadiene, copolyamide (Technora), polyimide (Ultem), aromatic polyesters (Vectran), poly(vinyl poly-p-phenylene-2,6- benzobisoxazole idene fluoride-co-hexafluoropropylene) (Viton), poly-p-phenylene- 2,6-benzobisoxazole (Zylon), and blends, mixtures, or alloys thereof.

18. The encapsulated curative composition of any one of claims 1-17, wherein the curative comprises Cu(II) carboxylates, Cu(II) chelates, metal alkoxides, bismuth carboxylates, zinc carboxylates, tin carboxylates, amine catalysts, heterocyclic amines, quaternary ammonium catalysts, dicyandiamides, diureas, diamines, blocked sulfonic acids, or combinations thereof.

19. The encapsulated curative composition of claim 18, wherein the metal carboxylates comprise ligands, wherein the ligands are selected from ethylenediamine (en); 2,2'- bipyridine (bipy); 1,10-phenanthroline (phen); oxalate (C2O42, oxalato),acetyl acetonate (acac ); diethylenetriamine (dien); EDTA (ethylenediaminetetraacetate); or combinations thereof.

20. The encapsulated curative composition of claim 19, wherein the metal carboxylate and ligands are bound to the carrier through hydrogen bonds.120903.000070\4918-6656-1929.1 - 37 -21. The encapsulated curative composition of any one of claims 1-18, wherein the curative comprises Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K- Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2- ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.

22. The encapsulated curative composition of any one of claims 1-21, further comprising accelerators.

23. The encapsulated curative of any one of claims 1-21, wherein the shell is formed from monomers of epoxy and thermoplastic polymers comprising polyester, polyurethane, or combinations thereof.

24. The encapsulated curative of claim 23, wherein the shell is formed from epoxy monomers selected from Epon 1001, Epon 1004, Epon 1007, or a combination thereof.

25. The encapsulated curative of claim 23, wherein the shell is formed from styrenic polymers and copolymers, polamides, polyimides, polyethylene (PE: LDPE, LLDPE, HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS, including HIPS, EPS), polyethylene terephthalate (PET, PETG), polyamide / Nylon (PA6, PA66, others), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), styreneacrylonitrile (SAN), PC / ABS blends, and combinations thereof.

26. The encapsulated curative of any one of claims 1-25, wherein the surfactant is selected from ionic surfactants and non-ionic surfactants.120903.000070\4918-6656-1929.1 - 38 -27. The encapsulated curative of any one of claims 1-26, wherein the surfactant is selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxycholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof.

28. The encapsulated curative of any one of claims 1-27, wherein the surfactant is present in an amount of from 1-20% by weight.

29. The encapsulated curative of claim 27, wherein the PVP comprises K-grade homopolymers selected from K-17, K-30, K-60, K-90, or combinations thereof.

30. The encapsulated curative of any one of claims 1-29, wherein the surfactant is on or in the shell.

31. The encapsulated curative of any one of claims 1-30, wherein the shell is about 10% w / w of the encapsulated curative particles.

32. The encapsulated curative of any one of claims 1-31, wherein the encapsulated curative further comprises microwave susceptors, Rf susceptors, or both.

33. The encapsulated curative of claim 32, wherein the encapsulated curative comprises a susceptor selected from fullerene compounds, graphene, graphite oxide, nanocrystalline cellulose single- single-walled carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more ferrous metals, oxides of one or more ferrous metals. SPIONS, one or more non-ferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, or more combinations thereof.Curable Resin34. A curable resin composition comprises the encapsulated curative composition of any one of claims 1-33 and a thermosetting resin.120903.000070\4918-6656-1929.1 - 39 -35. The curable resin composition of claim 34, wherein the thermosetting resin comprises acrylates, silane-terminated polymers, isocyanates, polyurethane, polyurea, epoxy, amino crosslinking resins, or combinations thereof.

36. The curable resin composition of any one of claims 34-35, wherein the melt temperature of the thermosetting resin is within 20 °C of the latency temperature of the shell.

37. The curable resin composition of any one of claims 34-36, wherein the thermosetting resin of the curable resin composition is the same thermosetting resin of the shell of the encapsulated curative.

38. The curable resin composition of any one of claims 34-37, wherein the viscosity of the curable resin composition is from 500 to 30,000 mPa s at 23°C.

39. The curable resin composition of any one of claims 34-38, wherein the curable resin composition is storage stable at 25°C for up to 24 months.

40. The curable resin composition of any one of claims 34-39, wherein the curable resin composition is fully cured after activation at 80-180°C within 30 minutes.Curing the resin41. A process for initiating a chemical reaction, comprising activating the encapsulated curative in the curable resin composition of any one of claims 34 to 40.

42. The process of claim 41, wherein the activation step comprises a thermal step selected from oven heating, infrared heating, induction heating, contact heating, and combinations thereof.

43. The process of claim 41, wherein the activation step comprises treatment with UV light, IR light, or a combination thereof.

44. The process of claim 41, wherein the activation step comprises heating the composition to a temperature of about 50 °C to about 200 °C.120903.000070\4918-6656-1929.1 -40 -45. The process of claim 44, wherein the activation step comprises maintaining the temperature of the composition at a temperature for a period of about 1 to 1,000 minutes.

46. The process of claim 41, wherein the activation step comprises impinging the bulk reaction mixture with at least one frequency of RF radiation and / or at least one frequency of MW radiation.

47. The process of claim 46, wherein the impinging of at least one frequency of RF radiation and / or at least one frequency of MW radiation is performed periodically, wherein the period is regular or irregular.

48. The process of claim 46, wherein the activation step comprises impinging the bulk reaction mixture with electromagnetic radiation frequencies ranging from about 50 MHz to about 30 GHz.

49. The process of claim 48, wherein the electromagnetic radiation frequency ranges from about 915 MHz to about 2.45 GHz.

50. The process of claim 49, wherein the electromagnetic radiation has a power in the range of about 1 W to about 10,000 W.

51. The process of claim 48, wherein the electromagnetic radiation is impinged for about 10 seconds to about 60 minutes.

52. The process of claim 51, wherein the chemical reaction is a polymerization reaction.120903.000070\4918-6656-1929.1 -41 -Method of making an encapsulated curative53. A method of making an encapsulated curative, comprising the steps of:mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal aluminum silicate curative composition, mixing the curative composition with a resin solution in water-soluble solvents, andmixing the curative composition and resin solution with an aqueous solution comprising a surfactant to disperse the curative composition particles in water, and depositing the resin onto the curative composition particle by solvent deposition to form the encapsulated curative.

54. The method of claim 53, wherein the resin is deposited onto the curative composition to form the encapsulated curative by:fluidize the curative composition in a fluid bed coater to form fluidized particles, andforming a uniform film or layered coating on the fluidized particles by spraying a resin solution onto the fluidized particles.

55. The method of claim 54, wherein the resin solution is sprayed upwards onto the fluidized particles.

56. The method of claim 54, wherein the resin solution is sprayed downwards onto the fluidized particles.

57. The method of claim 53, wherein the resin is deposited onto the curative composition to form the encapsulated curative by removing the aqueous solution.

58. The method of claim 53, wherein the resin is deposited onto the curative composition to form the encapsulated curative by spray drying.

59. The method of claim 53, wherein the resin comprises a polymer or polymer precursor dissolved or dispersed in a solvent, and deposited resin forms a polymer shell to encapsulate the curative composition particle.120903.000070\4918-6656-1929.1 -42 -60. The method of claim 59, wherein the polymer shell is created through a fluid bed coating process.

61. A method of making an encapsulated curative, comprising the steps of:mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth to form a metal aluminum silicate curative composition, mixing the curative composition with a resin solution in an organic solvent, andspray drying the mixture of the curative composition and resin solution to form an encapsulated curative with a shell.

62. The method of any one of claims 53-61, comprising the steps of: mixing a sodium aluminum silicate with copper 2-ethyl hexanoate to form a Cu(II) aluminum silicate.

63. The method of any one of claims 53-60, wherein the surfactant is selected from ionic surfactants and non-ionic surfactants.

64. The method of claim 63, wherein the surfactant is selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxycholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof.

65. The method of claim 64, wherein the PVP comprises K-grade homopolymers selected from K-17, K-30, K-60, K-90, or combinations thereof.

66. The method of any one of claims 53-60 and 62-65, wherein the surfactant is on or in the shell.

67. The method of any one of claims 53-66, wherein the shell is about 10% w / w of the encapsulated curative particles.

68. The method of any one of claims 53-67, wherein the encapsulated curative further comprises microwave susceptors, Rf susceptors, or both.120903.000070\4918-6656-1929.1 -43 -69. The method of claim 68, wherein the encapsulated curative comprises a susceptor selected from fullerene compounds, graphene, graphite oxide, nanocrystalline cellulose single- single-walled carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more ferrous metals, oxides of one or more ferrous metals. SPIONS, one or more nonferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, or more combinations thereof.

70. The method of claim 53, wherein the sodium aluminum silicate comprises micro or mesoporosity suitable for the adsorption of metal carboxylates.

71. The method of any one of claims 62, wherein the copper 2 -ethyl hexanoate is present in an amount effective to form Cu(II) surface complexes immobilized on the aluminosilicate surface.

72. The method of any one of claims 53-71, wherein the resin solution comprises an epoxy resin, an acrylate resin, a polyurethane prepolymer, a benzoxazine, a cyanate ester, or combinations thereof.

73. The method of any one of claims 53-72, wherein the resin comprises an epoxy solution selected from EPON 100 IF, 1004F, 1007F, or combinations thereof.

74. The method any one of claims 53-60 and 62-73, wherein the surfactant is selected from anionic, cationic, nonionic, or amphoteric, and is present at a concentration sufficient to maintain a stable aqueous dispersion during the addition and solvent removal.

75. The method of any one of claims 53-74, wherein the solvent is removed by atmospheric evaporation under stirring, optionally assisted by mild heating and / or reduced pressure to deposit a continuous or semi -continuous resin shell.

76. The method of any one of claims 53-75, wherein the encapsulated particles have a D50 particles size from 1-1000 microns.120903.000070\4918-6656-1929.1 -44 -Non-encapsulated curative77. A curative composition, comprising a plurality of carrier particles and a curative, wherein the plurality of carrier particles comprise particles characterized as organic, inorganic, microporous, mesoporous or any combination thereof, wherein the curative:(i) resides within one or more of the carrier particles,(ii) resides within the interstitial spaces between the plurality of carrier particles, or(iii) is bound to a surface of one or more of the carrier particles.

78. The curative composition of claim 77, wherein the carrier particles have an average particle size of 1 - 1,000 microns.

79. The curative composition of any one of claims 77-78, wherein the carrier particles comprises at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, an oligomer, or combinations thereof.

80. The curative composition of any one of claims 77-79, wherein the inorganic metal salt comprises precipitated silica, aluminum silicate, neutral aluminum oxide, basic and acidic aluminum oxide, silane functionalized silicates, aluminum silicates, or combinations thereof.

81. The curative composition of any one of claims 77-80, wherein the curative comprises Cu(II) carboxylates, Cu(II) chelates, metal alkoxides, bismuth carboxylates, zinc carboxylates, tin carboxylates, amine catalysts, heterocyclic amines, quaternary ammonium catalysts, dicyandiamides, diureas, diamines, blocked sulfonic acids, or combinations thereof.

82. The curative composition of claim 81, wherein the metal carboxylates comprise ligands, wherein the ligands are selected from ethylenediamine (en); 2,2' -bipyridine (bipy); 1,10-phenanthroline (phen); oxalate (C2O42, oxalato), acetyl acetonate (acac ); diethylenetriamine (dien); EDTA (ethylenediaminetetraacetate); or combinations thereof.120903.000070\4918-6656-1929.1 -45 -83. The curative composition of any one of claims 77-81, wherein the curative comprises Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K- Kat XK-651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.Amalgamated curative84. The curative composition of any one of claims 77-83, further comprising a matrix that holds the carrier particles together.

85. The curative composition of claim 84, wherein the matrix is formed from monomers of epoxy and thermoplastic polymers comprising polyester, polyurethane, or combinations thereof.

86. The curative composition of claim 85, wherein the matrix is formed from epoxy monomers selected from Epon 1001, Epon 1004, Epon 1007, or a combination thereof.

87. The curative composition of claim 86, wherein the matrix is formed from styrenic polymers and copolymers, polamides, polyimides, polyethylene (PE: LDPE, LLDPE, HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS, including HIPS, EPS), polyethylene terephthalate (PET, PETG), polyamide / Nylon (PA6, PA66, others), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), styreneacrylonitrile (SAN), PC / ABS blends, and combinations thereof.

88. The curative composition of any one of claims 84-87, further comprising a surfactant.120903.000070\4918-6656-1929.1 -46 -89. The curative composition of claim 88, wherein the surfactant is selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxycholate, Triton X-100, Pluronic F-127, andBrij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof.Method of Making a non-encapsulated curative composition90. A method of making a curative composition, comprising the steps of:mixing a sodium aluminum silicate with metal salts or metal ligands of copper, iron, tin, or bismuth.

91. The method of claim 90, comprising the steps of: mixing a sodium aluminum silicate with copper 2-ethyl hexanoate to form a Cu(II) aluminum silicate.

92. A method of making a curative composition, comprising the steps of:mixing a sodium aluminum silicate with Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K-Kat XK- 651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.120903.000070\4918-6656-1929.1 -47 -93. The method of claim 92, further comprising the step of spray coating, solvent deposition with agitation, and ultrasonication of the sodium aluminum silicate with Cu(II) 2-ethyl hexanoate, Cu(II) acetyl acetonate, K-Kat 670, K-Kat 648, TIB KAT 223 (dioctyltin diacetyl acetonate), stannous (II) bis(2-ethylhexanoate) (stannous octoate), N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine (polycat), TBAF (tetra butyl ammonium fluoride), titanium acetyl acetonate (Tyzor AA105), K-Kat XK-661, DBTDL (Dibutyltin dilaurate), K-Kat XK-682 (bismuth), K-Kat XK-635 (zinc), K- Kat XK-651 (bismuth), Nacure PC-100, K Pure CXC-1765, imidazole, dicyandiamide, diurea, diamino diphenyl sulfone, or combinations thereof.Post functionalization94. The method of any one of claims 53-76, further comprising the step of organophilization of the surface of the core before forming the shell.

95. The method of claim 94, wherein the step of organophilization comprises silanization.

96. The method of claim 94, wherein the step of organophilization comprises treating the core with one or more organosilane coupling agents and / or grafting of organic polymers or oligomers.

97. The method of claim 94, wherein the step of organophilization comprises treatment of the core with 3 -Aminopropyltri ethoxy silane (APTES),3 -Aminopropyltrimethoxy silane, N-(2-Aminoethyl)-3 -aminopropyltrimethoxy silane, Epoxy / glycidoxy silanes (epoxy, urethane, acrylic systems; fillers pretreatment), 3 -Glycidoxypropyltrimethoxy silane (GPTMS, GLYMO),3-Glycidoxypropyltriethoxysilane, tetraethyl orthosilicate (TEOS),2-(3,4-Epoxycy cl ohexyl)ethyltrimethoxy silane, Methacryloxy / acryloxy silanes (unsaturated polyester, acrylics, optical fibers),3 -Methacryloxypropyltrimethoxy silane (MEMO),3 -Methacryloxypropyltri ethoxy silane, Mercapto silanes (rubber, metal adhesion, sulfur chemistry), 3-Mercaptopropyltrimethoxysilane,3-Mercaptopropyltriethoxysilane, (3-Mercaptopropyl)methyldimethoxysilane, 3- Isocyanatopropyltriethoxysilane, or a combination thereof.120903.000070\4918-6656-1929.1 -48 -98. The method of claim 94, wherein the step of organophilization comprises treatment of the core with propyltriethoxysilane, tetraethyl orthosilicate (TEOS), or combinations thereof.

99. The method of claim 95, wherein the loading of the organosilane is 0.5-3 mmol of functional groups per gram of carrier.

100. The method of claim 95, wherein the core comprises about 5-25 wt% organic content on the core.120903.000070\4918-6656-1929.1 -49 -

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