Nanoparticles and microparticles that enhance physical properties of formulations, preparation and end products

Abstract

In one aspect, the present invention relates to a plurality of matrix particles comprising a core and optionally at least one shell wherein the core comprises: (i) a matrix material wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties; (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material; and (iii) at least one releasable ingredient, where the at least one releasable ingredient is embedded in the matrix material, where the at least one releasable ingredient is capable of physically or chemically affecting a physical or chemical composition in contact with the plurality of matrix particles; and wherein the at least one shell comprises: (iv) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and (v) at least one releasable component wherein the at least one releasable component is embedded in the at least one shell wherein the at least one releasable component is capable of physically or chemically influencing a physical or chemical composition in contact with the plurality of matrix particles.

Description

Cross Reference to Related Applications

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application 63 / 496,724, filed April 18, 2023, which is incorporated by reference herein in its entirety for any and all purposes. TECHNICAL FIELD

[0002] The nanoparticles and microparticles of the present invention serve as carriers for more efficient delivery of nanomaterials to sealants, coatings, composites, adhesives, and other polymeric products. Specifically, the present invention relates to matrix particles carrying nanomaterials, including metals and their chemical products, carbon nanostructures such as graphene and carbon nanotubes, for improving physical, electrical, thermal, chemical, and conductive properties, or simply to minimize the amount of the nanomaterials. Optionally, crosslinking chemicals can be incorporated into the particles simply on the surface or as ligands or oligomer-like structures that are able to even further enhance the physical properties. In one embodiment, the matrix particles as described above are used as nanoparticle and / or microparticle carriers to be blended or mixed into a polymeric or reaction precursor mixture for further processing.

[0003] Generally, and in one aspect, the present invention relates to matrix particles comprising a matrix material as defined below, a susceptor, and a releasable ingredient. In some embodiments, the particles are in a core-shell configuration, or are simply a core. The core is able to change its physical or chemical form, which allows the release of the releasable ingredient. When the particles are in a core-shell configuration, there can be one or more shells. The susceptor can be in the shell or in one or more shells. Similarly, the releasable ingredient can be in the shell or in one or more shells. The shell is thus a physically or chemically changeable material, such as an oligomer or a polymeric material. The presence of a susceptor in the matrix particles is optional. Such matrix particles are mixed in a physical or chemical composition of interest that needs to be physically or chemically affected by mixing with the matrix particles and applying an external force, such as radiofrequency or heat, that will change the matrix particles and release the releasable ingredient into the physical or chemical mixture or composition. BACKGROUND

[0004] In composite manufacturing, eliminating total heating provides higher throughput and eliminates the need to cool down the parts or molded material from the mold before removing the parts or molded material from the mold. Currently, polymerization can be initiated by dual component mixing to obtain a complete reaction system, by photo-activation of catalysts, or by total heating of the composition or similar. Each of these ways has limitations by default. Total heating takes a long time, uses maximum amount of energy and associated complex equipment, and due to inherent stress generated by polymerization, through heating and cooling, results in limited performance of the remaining material. Total heating cannot be used in adhesive applications of elastomer substrates with glass transition temperature below room temperature. Dual component mixing can have the same or worse complexity and requires complex mixing or metering equipment to achieve uniform curing and proper mixing ratio separately. Light is by default limited to transparent objects, can only cure thin objects, requires special packaging to block light, excess catalyst amount is typically over 1% and typically excess heat energy is input, and again complex equipment is required. On the other hand, active catalyst and co-catalyst embedded in the matrix particles improve the shelf life of the product. For example, in B-stage products such as thermoset prepreg and film adhesive, to improve shelf life and usable time, the product is kept frozen until use.

[0005] In industrial manufacturing or processing, it is desirable to not use total heating, to cure larger objects on demand like with light, to not use complex curing equipment, to eliminate the need for complex and metal-based molding equipment, and to minimize catalyst loading and limited pot life of two-part systems or two-part systems.

[0006] In adhesives, total heating limits the use of thick substrates with higher glass transition temperature. Higher molecular weight materials present challenges in accepting higher loading of fillers or reinforcing materials such as milled carbon fibers and glass fibers. Using low molecular weight materials will enable higher filler content to be used. Uniform mixing of fillers and higher performance without rheological issues will be advantages of using low molecular weight materials.

[0007] As mentioned above, chemical activation through opaque objects is generally limited unless the object is sufficiently transparent to allow substantial transmission of light. A technique is needed that can penetrate opaque materials, especially over substantial distances. This would provide new capabilities to initiate polymerization to varying degrees in objects filled with various fillers without the need for heating and, if even possible, without the limitations of light transmission.

[0008] As exhibited by the prior art, the release of the constituents in the chemical reaction must be caused by the external environment of the chemical reaction chamber, not by events caused within the particle. This is similar to bulk heating, or if external light is used, it will be limited by the thin dimension.

[0009] In general, it is necessary to activate chemical reactions and eliminate total heating, minimize energy use, minimize materials and catalyst use to achieve the required high-speed chemical reactions, eliminate equipment complexity and minimize its cost and space, minimize or eliminate invasive procedures and achieve on-demand activation.

[0010] Incorporating nanomaterials into compositions can achieve a number of desired effects, which are then realized as final performance products. The functional materials and their formation or the effects of covalent bonds, hydrogen, and van der Waals forces can individually achieve significantly increased toughness, elasticity, strength, wear resistance, product life, environmental resistance, etc.

[0011] Importantly, the addition of nanomaterials is often fraught with physical, chemical, technological, and economic challenges.

[0012] In particular, nanomaterials (such as graphene or other sheet-like structures and / or nanotubes) have inherent properties that lead to their physical association, for example, agglomeration, attachment, and then network formation, all of which can result in limited detrimental effects. Chemical, van der Waals, and other associations ultimately lead to a significant increase in viscosity with increasing amounts of the nanomaterial, thus limiting the amount that can be added and consequently the range of desired effects to be incorporated into the composition. Carbon nanotubes are among the nanomaterials most limited by these overall effects. Therefore, this can particularly limit the total amount of nanomaterial that can be incorporated or the total amount required to achieve a specific effect.

[0013] The latter effect also limits the processing of compositions, not just the amount of material that can be incorporated. For example, the shear effect limits pumping and mixing or blending because the amount of energy required increases significantly, nanomaterials wear down equipment parts, heat accumulates, decomposes components, and / or triggers a variety of undesirable chemical and physical effects.

[0014] Economically, even if the former is overcome to any extent, unnecessary and more expensive amounts of material can be added to achieve the desired effect, which often makes many applications uneconomical and or limits overall economic application in the widest market.

[0015] In summary, it would be useful to find a more efficient and less restrictive way to utilize nanomaterials, especially nanotubes and graphene, without or at the same time greatly reducing the aforementioned limitations. Summary of the Invention

[0016] In one embodiment, the present invention relates to a plurality of matrix particles, the plurality of matrix particles including matrix particle A and / or matrix particle B:

[0017] The matrix particle A includes a core and optionally at least one shell.

[0018] wherein the core comprises:

[0019] (i) a matrix material, wherein the matrix material is capable of changing its physical and / or chemical properties completely or partially;

[0020] (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material; and

[0021] (iii) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the matrix material, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles, and

[0022] wherein the at least one shell comprises:

[0023] (iv) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and

[0024] (v) the at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the at least one shell, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles;

[0025] and

[0026] wherein the matrix particle B comprises a core and optionally at least one shell, wherein the core comprises:

[0027] (vi) a matrix material, wherein the matrix material is capable of changing its physical and / or chemical properties completely or partially; and

[0028] (vii) the at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the matrix material, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles; and

[0029] wherein the at least one shell comprises:

[0030] (viii) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and

[0031] (ix) the at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the at least one shell, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles; and

[0032] wherein the at least one susceptor component and / or the releasable ingredient is capable of being activated by radiofrequency (RF), microwave (MW) radiation, thermal activation, mechanical attrition, or a combination thereof.

[0033] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the matrix material is derived from and / or comprises an organic, monomeric, oligomeric, polymeric material, or a combination thereof.

[0034] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the at least one susceptor and / or the at least one releasable ingredient is selected from the group consisting of a fullerene compound, graphene, graphite oxide, nanocrystalline cellulose, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more ferruginous metals, oxides of one or more ferruginous metals, SPIONS, one or more non-ferruginous metals, oxides of one or more non-ferruginous metals, transition metals, transition metal oxides, silicon carbide-based materials, boron nitride, and one or more combinations thereof.

[0035] In one embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the at least one susceptor and / or the at least one releasable ingredient has a size in the range of about 0.1 nm to about 1000 pm, and optionally, the at least one susceptor and / or the at least one releasable ingredient is functionalized and / or non-functionalized.

[0036] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the at least one susceptor and / or the at least one releasable ingredient is in the at least one shell, and wherein the at least one susceptor and the at least one releasable ingredient is in direct or indirect contact.

[0037] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the matrix particles are partially or entirely coated in one or more layers of a deformable material or a force-modifying material, wherein, optionally, one or more of the layers contains the at least one susceptor and / or the at least one releasable ingredient.

[0038] In one embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the at least one releasable ingredient is a single chemical, a combination of chemicals, an organic chemical, and / or an inorganic chemical, and wherein the at least one releasable ingredient comprises one or more catalysts, co-catalysts, co-reactants, oxidizing agents, reaction-inhibiting compounds, accelerants, co-accelerants, fuels, explosives, or one or more combinations thereof.

[0039] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the at least one releasable ingredient is released when the matrix material or the shell is deformed, dissolved, melted, expanded, shrunk, ruptured, plasticized, solvated, affected by light, or one or more combinations thereof.

[0040] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the particles are further chemically surface modified via one or more chemical reactions, optionally comprising the at least one releasable ingredient, and then optionally forming a partial or complete coating.

[0041] In one embodiment, the present application is directed to a plurality of matrix particles as described above having a chemical functional group, wherein the at least one releasable ingredient comprises a chemically functional monomer, wherein the matrix material comprises a polymeric material, and optionally, the matrix particles are coated with a polymeric coating.

[0042] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein one or more variable matrix materials comprise a wax, one or more of the following: polymethyl methacrylate (PMMA), styrene, or one or more polymers or copolymers thereof.

[0043] In yet another embodiment, the present application is directed to a method of making a plurality of matrix particles as described above using method A, B, C, D, or a combination thereof, wherein:

[0044] (A) comprises emulsion polymerization, dispersion polymerization, and / or suspension polymerization; or

[0045] (B) comprises core-shell polymerization; or

[0046] (C) comprises copolymerization, wherein the copolymerization step comprises emulsion polymerization, dispersion polymerization, suspension polymerization, or a combination thereof;

[0047] (D) comprises the following steps:

[0048] (i) coating a polymeric microparticle with a material comprising a susceptor and a releasable ingredient,

[0049] (ii) encapsulating the microparticle with the susceptor and the releasable ingredient embedded therein with a monomeric, oligomeric, or polymeric or polymeric material, and / or

[0050] (iii) combining the susceptor and the releasable ingredient, and

[0051] (iv) embedding the susceptor and the releasable ingredient into an external pore on the surface of a porous microsphere or an internal pore in the core of the porous microsphere; or

[0052] combinations of A, B, C, and D.

[0053] In one embodiment, the present application relates to a method for affecting a chemical reaction or a method for releasing at least one releasable ingredient from a plurality of matrix particles, the method comprising:

[0054] (i) providing a bulk reaction mixture;

[0055] (ii) providing matrix particles as described above;

[0056] (iii) incorporating the plurality of matrix particles into the bulk reaction mixture; and

[0057] (iv) optionally incorporating the plurality of matrix particles into the bulk reaction mixture and impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particles;

[0058] heating the bulk reaction mixture comprising the plurality of matrix particles;

[0059] mechanically grinding the bulk reaction mixture comprising the plurality of matrix particles; or a combination thereof.

[0060] In another embodiment, the present application relates to a plurality of matrix particles as described above, wherein the CNTs are incorporated into the matrix particles by the method described above.

[0061] In yet another embodiment, the present application relates to an article of manufacture comprising a plurality of matrix particles as described above.

[0062] In one embodiment, the present application relates to an article of manufacture prepared as described above, which is wholly or partially:

[0063] (i) a polymerizable composition of at least one chemical substance or several polymerizable compositions;

[0064] (ii) a reinforced composite article;

[0065] (iii) a laminated article;

[0066] (iv) a rigid laminated article;

[0067] (v) a flexible laminated article;

[0068] (vi) a foam; or

[0069] (vii) a combination thereof.

[0070] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the composition is in whole or in part an adhesive, a sealant, a coating, a paint, an ink, a plastic, a molded plastic, a thermoset, a molded thermoset, or other polymeric forming composition.

[0071] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the releasable ingredient is a catalyst selected from the group consisting of transition metal complexes; transition metal alkoxides; bis(2- ethylhexanoato)tin(II); carboxylates, alkoxides, and complexes of tin, bismuth, zinc, titanium; a blocked super acid; dodecylbenzenesulfonic acid; dinonylnaphthalenesulfonic acid; N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine; an organic base; 1,8-diazabicyclo[5.4.0]undec-7- ene; 1,5-diazabicyclo[4.3.0]non-5); (1,4-diazabicyclo 2.2.2 octane); and combinations thereof.

[0072] In one embodiment, the present application is directed to a multi-layer polymeric composition comprising a first plurality of matrix particles as described above, and one or more additional plurality of matrix particles as described above disposed on the first matrix particles, thereby forming one or more layers of matrix particles.

[0073] In another embodiment, the present application is directed to a precursor, intermediate, or final monomeric, oligomeric, or polymeric composition comprising a plurality of matrix particles as described above, wherein the composition is solid state polymerized or prepared from a reactive hot melt formulation.

[0074] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the plurality of matrix particles comprise carbon nanotubes, wherein the carbon nanotubes are coated on and / or contained within the matrix particles.

[0075] In one embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the CNTs are incorporated into the plurality of matrix particles by a blending process.

[0076] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the matrix particles are further coated with a functional nanoparticle emulsion.

[0077] In yet another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the matrix particles are further coated with a mono-functional reactive material or a dual reactive material.

[0078] In one embodiment, the present application relates to a precursor, intermediate or final monomeric, oligomeric or polymeric composition comprising a plurality of matrix particles according to any one of the claims as described above; optionally wherein the composition is prepared from a functionalized polymer formulation, and optionally wherein the composition is prepared as a reactive blend with a non-reactive polymer or oligomer.

[0079] In another embodiment, the present application relates to a method for influencing a chemical reaction, the method comprising:

[0080] (i) providing a bulk reaction mixture;

[0081] (ii) providing a plurality of matrix particles as described above;

[0082] (ii) incorporating the plurality of matrix particles into the bulk reaction mixture, and impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particles;

[0083] heating the bulk reaction mixture comprising the plurality of matrix particles;

[0084] mechanically milling the bulk reaction mixture comprising the plurality of matrix particles; or a combination thereof;

[0085] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for solid state polymerization;

[0086] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for a reactive hot melt formulation;

[0087] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for a reactive blend with a non-reactive polymer or oligomer; or

[0088] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for a functionalized polymer formulation.

[0089] In yet another embodiment, the present application relates to a method of increasing the total loading of CNTs in a bulk physically or chemically variable composition by the method in the above.

[0090] In one embodiment, the present application relates to a method of maintaining a lower viscosity upon the addition of at least one additive to a bulk physically or chemically variable composition, the method comprising incorporating the at least one additive as at least one releasable ingredient into a plurality of matrix particles as described above, and incorporating the plurality of matrix particles into the bulk physically or chemically variable composition.

[0091] In another embodiment, the present application relates to a method for increasing the total loading of an additive in a bulk physically or chemically variable composition, the method comprising:

[0092] (i) providing the bulk physically or chemically variable composition;

[0093] (ii) incorporating the at least one additive as a releasable ingredient into a plurality of matrix particles as described above;

[0094] (ii) incorporating the plurality of matrix particles into the bulk physically or chemically variable composition, and shocking the bulk physically or chemically variable composition at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particles;

[0095] heating the bulk physically or chemically variable composition comprising the plurality of matrix particles;

[0096] mechanically grinding the bulk physically or chemically variable composition comprising the plurality of matrix particles; or a combination thereof;

[0097] Optionally wherein the bulk physically or chemically variable composition is a monomeric, oligomeric or polymeric composition for a reactive hot-melt formulation, an adhesive, a coating, a precursor or intermediate for a composite material, a combination thereof.

[0098] In yet another embodiment, the present application relates to a method of maintaining a lower viscosity upon the addition of at least one additive to a bulk physically or chemically variable composition, the method comprising the steps of:

[0099] (i) providing the bulk physically or chemically variable composition;

[0100] (ii) incorporating the at least one additive as a releasable ingredient into a plurality of matrix particles as described above;

[0101] (ii) incorporating the plurality of matrix particles into the bulk physically or chemically variable composition, and shocking the bulk physically or chemically variable composition at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particles;

[0102] heating the bulk physical or chemically variable composition comprising the plurality of matrix particles;

[0103] mechanically milling the bulk physical or chemically variable composition comprising the plurality of matrix particles; or a combination thereof;

[0104] Optionally wherein the bulk physical or chemically variable composition is a monomeric, oligomeric or polymeric composition for reactive hot melt formulations, adhesives, coatings, precursors or intermediates for composites, a combination thereof.

[0105] In another embodiment, the present application is directed to a plurality of matrix particles as described above, wherein the releasable ingredient is a catalyst for curing, polymerization, acrylate reaction, silane terminated polymer, hydrolysis, condensation, isocyanate trimerization, 1 K moisture cure isocyanate, melamine crosslinking system, 2K polyurethane, 1 K blocked isocyanate based polyurethane, epoxide, esterification and transesterification.

[0106] In one embodiment, the present application is directed to a matrix particle comprising:

[0107] (i) a matrix material, wherein the matrix is capable of changing its physical properties completely or partially;

[0108] (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material, and wherein the at least one susceptor component is capable of being heat activated by electromagnetic radiation; and

[0109] (iii) at least one releasable and / or activatable ingredient, which is embedded in the matrix and in proximity to the susceptor component, wherein the at least one releasable and / or activatable ingredient is capable of affecting a chemical reaction.

[0110] In another embodiment, the present application is directed to a matrix particle as described above, comprising one or more matrix suitable discrete zones, the discrete zones being in one or more shapes; wherein the discrete zones comprise a coating or a different layer; wherein each zone comprises from about zero to a plurality of susceptors and / or releasable ingredients; and wherein the matrix particle in the aggregate has at least one zone comprising a susceptor and at least one zone comprising a releasable ingredient.

[0111] In yet another embodiment, the present application is directed to a matrix particle as described above, wherein the matrix is derived from and / or contains organic, inorganic, monomeric, oligomeric, polymeric materials or a combination thereof.

[0112] In another embodiment, the present application is directed to a matrix particle as described above, wherein the at least one susceptor is selected from the group consisting of a fullerene compound, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more siderophores, oxides of one or more siderophores, superparamagnetic iron oxide (SPION), one or more non-siderophores, oxides of one or more non-siderophores, transition metals, transition metal oxides, silicon carbide-based materials, boron nitride, and one or more combinations thereof.

[0113] In yet another embodiment, the present application is directed to a matrix particle as described above, wherein the susceptor has a size in the range of about 0.1 nm to about 1000 pm.

[0114] In one embodiment, the present application is directed to a matrix particle as described above, wherein the susceptor comprises a functionalized susceptor, a non-functionalized susceptor, or both a functionalized and a non-functionalized susceptor.

[0115] In another embodiment, the present application is directed to a matrix particle as described above, wherein the susceptor is located at the geometric center of the matrix material in direct or indirect contact with the susceptor.

[0116] In yet another embodiment, the present application is directed to a matrix particle as described above, wherein the susceptor and / or the releasable ingredient is in the outer layer of the matrix particle, wherein the susceptor and the releasable ingredient are in direct or indirect contact.

[0117] In one embodiment, the present application is directed to a matrix particle as described above, wherein the matrix particle is partially or entirely coated in one or more layers of deformable material.

[0118] In another embodiment, the present application is directed to a matrix particle as described above, wherein the matrix particle is partially or entirely coated in one or more layers of deformable material, wherein one or more of the layers contain a susceptor and or a releasable ingredient.

[0119] In another embodiment, the present application is directed to a matrix particle as described above, wherein the matrix material does not contain a susceptor or a releasable ingredient.

[0120] In one embodiment, the present application is directed to a matrix particle as described above, wherein the at least one releasable and / or activatable ingredient is a single chemical, a combination of chemicals, an organic chemical, and / or an inorganic chemical.

[0121] In another embodiment, the present application is directed to a matrix particle as described above, wherein the chemical composition comprises one or more catalysts, co-catalysts, co-reactants, oxidizing agents, reaction-inhibiting compounds, accelerants, fuels, explosives, or one or more combinations thereof.

[0122] In yet another embodiment, the present application is directed to a matrix particle as described above, wherein the releasable component is released when the matrix is deformed, dissolved, melted, expanded, contracted, ruptured, plasticized, solvated, or one or more combinations thereof.

[0123] In one embodiment, the present application is directed to a matrix particle as described above, wherein the electromagnetic radiation frequency is in the range of about 300 MHz to about 300 GHz.

[0124] In another embodiment, the present application is directed to a matrix particle as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz.

[0125] In yet another embodiment, the present application is directed to a matrix particle as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz and / or the power is in the range of 1 W - 10,000 W.

[0126] In another embodiment, the present application is directed to a matrix particle as described above, wherein the matrix particle is subjected to the electromagnetic radiation frequency as described above for 10 seconds to 60 minutes.

[0127] In one embodiment, the present application is directed to a matrix particle as described above, wherein the matrix is optionally loaded with a carrier comprising a metal, ceramic, or glass.

[0128] In another embodiment, the present application is directed to a matrix particle as described above, wherein the particle is further chemically surface modified via one or more chemical reactions, optionally containing a releasable component, optionally then forming a partial or complete coating.

[0129] In yet another embodiment, the present application is directed to a matrix particle as described above, further having a chemical functional group.

[0130] In one embodiment, the present application is directed to a matrix particle as described above, wherein the releasable component comprises a chemical functional monomer, wherein the matrix material comprises a polymeric material, and optionally, the matrix particle is coated with a polymeric coating.

[0131] In another embodiment, the present application is directed to a method for making a matrix particle as described above, the method steps comprising:

[0132] (i) emulsion suspension, dispersion suspension and / or suspension polymerization, or

[0133] (ii) core-shell polymerization.

[0134] In yet another embodiment, the present application relates to a method for preparing a matrix particle as described above, the method comprising:

[0135] (i) coating polymeric microparticles with a material comprising a susceptor and a releasable ingredient,

[0136] (ii) encapsulating microparticles with the susceptor and the releasable ingredient embedded therein with a monomeric, oligomeric or polymeric material,

[0137] (iii) combining the susceptor and the releasable ingredient, and / or

[0138] (iv) embedding the susceptor and the releasable ingredient into external pores on the surface of a porous microsphere or into internal pores in the core of the porous microsphere.

[0139] In one embodiment, the present application relates to a method for preparing a matrix particle as described above, the method steps comprising copolymerization, wherein the copolymerization step comprises emulsion polymerization, dispersion polymerization, suspension polymerization or a combination thereof.

[0140] In one embodiment, the present application relates to a method for affecting a chemical reaction, the method comprising:

[0141] (i) providing a bulk reaction mixture;

[0142] (ii) providing a matrix particle as described above; and

[0143] (iii) incorporating the matrix particle into the bulk reaction mixture.

[0144] In another embodiment, the present application relates to a method for affecting a chemical reaction as described above, the method further comprising:

[0145] (iv) impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle.

[0146] In yet another embodiment, the present application relates to a method for affecting a chemical reaction as described above, wherein impinging with RF radiation of at least one frequency and / or MW radiation of at least one frequency is carried out periodically, wherein the periodicity is regular or irregular.

[0147] In one embodiment, the present application is directed to a method for affecting a chemical reaction as described above, wherein the electromagnetic radiation has a wavelength in the range of about one meter to one millimeter; and a frequency in the range of 50 MHz to 30 GHz.

[0148] In another embodiment, the present application is directed to a method for affecting a chemical reaction as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz.

[0149] In another embodiment, the present application is directed to a method for affecting a chemical reaction as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz and / or the power is in the range of 1 W - 10,000 W.

[0150] In one embodiment, the present application is directed to a method for affecting a chemical reaction as described above, wherein the reaction is a polymerization reaction.

[0151] In another embodiment, the present application is directed to a method for releasing a releasable ingredient from a matrix particle as described above, the method comprising:

[0152] (a) dispersing the matrix particle in a bulk reaction mixture; and

[0153] (b) impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle.

[0154] In another embodiment, the present application is directed to a matrix particle as described above, wherein the one or more variable matrix materials include a wax, one or more of: polymethyl methacrylate (PMMA), styrene, or one or more polymers or copolymers thereof.

[0155] In one embodiment, the present application is directed to a matrix particle as described above, wherein the at least one releasable chemical ingredient comprises an activator or catalyst.

[0156] In another embodiment, the present application is directed to a matrix particle as described above, wherein the catalyst includes one or more of: copper acetylacetonate, copper 2-ethylhexanoate, ferrocene, dimethylaminomethyl ferrocene, or one or more combinations thereof.

[0157] In yet another embodiment, the present application is also directed to an article of manufacture prepared using the method as described above.

[0158] In yet another embodiment, the present application is directed to an article of manufacture prepared using the method as described above, the article of manufacture being wholly or partially:

[0159] (i) at least one polymerizable composition of chemical species or several polymerizable compositions of chemical species;

[0160] (ii) a reinforced composite article;

[0161] (iii) a laminated article;

[0162] (iv) a rigid laminated article;

[0163] (v) a flexible laminated article;

[0164] (vi) a foam; or

[0165] (vii) combinations thereof.

[0166] In one embodiment, the present application is also directed to a composition comprising the matrix particles as described above, wherein the composition is in whole or in part an adhesive, a sealant, a coating, a paint, an ink, a plastic, a molded plastic, a thermoset plastic, a molded thermoset plastic, or other polymeric forming composition.

[0167] In another embodiment, the present application is directed to the matrix particles as described above, wherein the releasable and / or activatable ingredient is a catalyst selected from the group consisting of transition metal complexes; transition metal alkoxides; bis(2- ethylhexanoato)tin(II); carboxylates, alkoxides, and complexes of tin, bismuth, zinc, titanium; a blocked super acid; dodecylbenzenesulfonic acid; dinonylnaphthalenesulfonic acid; N,N',N"- tris(dimethylaminopropyl)hexahydrotriazine; an organic base; 1,8-diazabicyclo[5.4.0]undec-7- ene; 1,5-diazabicyclo[4.3.0]non-5); (1,4-diazabicyclo 2.2.2 octane); and combinations thereof.

[0168] In one embodiment, the present application is directed to the matrix particles as described above, wherein the matrix particles comprise carbon nanotubes, wherein the carbon nanotubes are coated on the matrix particles and / or are contained in the matrix particles.

[0169] In one embodiment, the present application is directed to the matrix particles as described above, wherein the CNTs are incorporated into the matrix particles by a co-mingling process.

[0170] In one embodiment, the present application is directed to the matrix particles as described above, wherein the matrix particles are further coated with a functional nanoparticle emulsion.

[0171] In one embodiment, the present application is directed to the matrix particles as described above, wherein the matrix particles are further coated with a monofunctional reactive material.

[0172] In one embodiment, the present application relates to a matrix particle as described above, wherein the matrix particle is further coated with a dual reactive material.

[0173] In one embodiment, the present application relates to a precursor, intermediate or final monomeric, oligomeric or polymeric composition comprising a matrix particle according to the above.

[0174] In one embodiment, the present application relates to a precursor, intermediate or final monomeric, oligomeric or polymeric composition comprising a matrix particle according to the above, wherein the composition is prepared from a functionalised polymer formulation.

[0175] In one embodiment, the present application relates to a precursor, intermediate or final monomeric, oligomeric or polymeric composition comprising a matrix particle according to the above, wherein the composition is prepared as a reactive blend with a non-reactive polymer or oligomer.

[0176] In one embodiment, the present application relates to a method for influencing a chemical reaction, the method comprising:

[0177] (i) providing a bulk reaction mixture;

[0178] (ii) providing a matrix particle according to any of the preceding claims;

[0179] (iii) incorporating the matrix particle into the bulk reaction mixture; and

[0180] (iv) impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle;

[0181] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for solid state polymerisation.

[0182] In one embodiment, the present application relates to a method for influencing a chemical reaction, the method comprising:

[0183] (i) providing a bulk reaction mixture;

[0184] (ii) providing a matrix particle according to any of the preceding claims;

[0185] (iii) incorporating the matrix particle into the bulk reaction mixture; and

[0186] (iv) impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle;

[0187] wherein the bulk reaction mixture is a monomeric, oligomeric or polymeric composition of precursors or intermediate monomers for a reactive hot melt formulation.

[0188] In one embodiment, the present application relates to a method for influencing a chemical reaction, the method comprising:

[0189] (i) providing a bulk reaction mixture;

[0190] (ii) providing substrate particles as described above;

[0191] (iii) incorporating the substrate particles into the bulk reaction mixture; and

[0192] (iv) impacting the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to heat-activate the susceptor component embedded within the substrate particles;

[0193] wherein the bulk reaction mixture is a monomeric, oligomeric or polymeric composition of precursors or intermediate monomers for a functionalized polymer formulation.

[0194] In one embodiment, the present application relates to a method for influencing a chemical reaction, the method comprising:

[0195] (i) providing a bulk reaction mixture;

[0196] (ii) providing substrate particles as described above;

[0197] (iii) incorporating the substrate particles into the bulk reaction mixture; and

[0198] (iv) impacting the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to heat-activate the susceptor component embedded within the substrate particles;

[0199] wherein the bulk reaction mixture is a monomeric, oligomeric or polymeric composition of precursors or intermediate monomers for a reactive blend with a non-reactive polymer or oligomer.

[0200] In one embodiment, the present application relates to a method as described above, wherein the impacting with RF radiation of at least one frequency and / or MW radiation of at least one frequency is performed periodically, wherein the periodicity is regular or irregular.

[0201] In another embodiment, the present application relates to a method as described above, wherein the electromagnetic radiation has a wavelength in the range of about one meter to one millimeter; and a frequency in the range of 50 MHz to 30 GHz.

[0202] In yet another embodiment, the present application is directed to a method as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz.

[0203] In one embodiment, the present application is directed to a method as described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2.450 MHz and / or the power is in the range of 1 W - 10,000 W.

[0204] In another embodiment, the present application is directed to a method as described above, wherein the electromagnetic radiation is impinged for a period of time in the range of 10 seconds to 60 minutes.

[0205] In yet another embodiment, the present application is directed to a method as described above, wherein the reaction is a polymerization reaction.

[0206] In one embodiment, the present application is directed to a method for increasing the total loading of CNTs in a reaction mixture by a method as described above.

[0207] In one embodiment, the present application is directed to a method for maintaining a lower viscosity when adding an additive to a reaction mixture, the method comprising incorporating the additive into a matrix particle as described above, and incorporating the matrix particle into the bulk reaction mixture.

[0208] In one embodiment, the present application is directed to a method for increasing the total loading of an additive in a chemical reaction, the method comprising:

[0209] (i) providing a bulk reaction mixture;

[0210] (ii) providing a matrix particle comprising an additive as described above;

[0211] (iii) incorporating the matrix particle into the bulk reaction mixture; and

[0212] (iv) impinging the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle;

[0213] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for a reactive hot melt formulation.

[0214] In one embodiment, the present invention relates to a method of maintaining lower viscosity when adding an additive to a reaction mixture, the method comprising reducing the van der Waals forces between the additive and the bulk reaction mixture, comprising the steps of incorporating the additive into a matrix particle as described above, incorporating the matrix particle into the bulk reaction mixture, and impacting the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the susceptor component embedded within the matrix particle;

[0215] wherein the bulk reaction mixture is a precursor or intermediate monomeric, oligomeric or polymeric composition for a reactive hot melt formulation.

[0216] Surprisingly, it has been found that nanoparticles and microparticles can be used as carriers for more efficient delivery of nanomaterials into sealants, coatings, composites, adhesives and other polymeric products. Of particular interest is the achievement of physical properties of the final composition and or physical product, including but not limited to thermal and electrical conductivity, improved and or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy damping, etc. as well as improved or controlled product life and or failure.

[0217] The present invention specifically, but not exclusively, nanoparticles and microparticles carrying a layer of nanomaterial, filled with nanomaterial or otherwise filled with nanomaterial, the nanomaterial including metals and their chemical products, graphene, nanotubes and similar structures, to benefit from improved physical, electrical, conductive and other similar properties, for example, to minimize the need for more significant amounts of the nanomaterial.

[0218] Optionally, cross-linking chemistry can be incorporated into or on the surface of the particles simply using surface chemistry or as ligands or oligomer-like structures capable of even further enhancing the physical properties.

[0219] Specifically, incorporation and or coating of polymer-based particles can be carried out within polymer-based particles containing nanomaterials such as nanotubes or similar structures, especially, for example, carbon nanotubes and or graphene or similar structures. This basic concept is especially helpful to limit the total amount of material needed, can provide a large surface area containing the structures through which dispersion forces are dispersed, limit agglomeration, etc. In the case of nanoparticles and or microparticles coated with van der Waals and other physical or chemical force-improving coatings, these effects can be further improved and or amplified and controlled as needed.

[0220] The literature documents coating of the particles or individual nanotubes with, for example, carbon nanotubes. Here, we distinguish by coating the particles with nanotubes, then force-improving composition coating, incorporating more than one and preferably three or more nanotubes and or then force-improving composition coating.

[0221] Optionally, if any chemical functionality is used for subsequent reactions or physical effects, it can be incorporated into the particles and or their coatings. Examples of chemical reactions are myriad and are not limited, but include crosslinking and or polymerization reactions. Physical effects can include ligand, polymer and or oligomer structures, such as physically bound to a surrounding polymer matrix, or in the case of metal or soap ligands, emulsions, dispersions, etc. dispersed or contained in solvents, water or other media. Optionally included - see U.S. Patent Application 18 / 055,302 to Malofsky et al., incorporated by reference as if fully set forth herein - catalysts, co-catalysts, promoters, fuels, high energy materials, etc. are included in the invention.

[0222] It is another object of the invention to provide polymeric nanoparticles and microparticles having functional groups on the surface that can irreversibly / reversibly reduce when a composition containing the polymeric microparticles is applied to a composition containing sealants, composites, adhesives, other polymeric products, etc.

[0223] It is another object to provide functional groups that are capable of non-covalent bonding, such as hydrogen bonding or van der Waals forces, when a composition containing the polymeric microparticles is applied to a composition of sealants, composites, adhesives and other polymeric products.

[0224] In general, these functional nanoparticles and microparticles are a versatile platform with tunable properties that can be tailored to meet specific application requirements. These functional nanoparticles and microparticles can be used in many applications, including but not limited to adhesives, composites, laminates, sealants, coatings, inks, plastics, etc. in many end products in many consumer, industrial and or medical applications.

[0225] Functional nanomicroparticles include latex particles, nanogel and microgel particles, colloidal particles, including but not limited to colloidal particles composed of polymer chains dispersed in water or other solvents. Also included are microgel particles that can swell or shrink in response to changes in their environment.

[0226] Functional microparticles containing reactive functional groups, such as carboxylic acids, amino groups, thiols, epoxides, acrylics, isocyanates, can be crosslinked with other functionalized particles.

[0227] In coatings, crosslinked polymeric microparticles are used to produce compositions containing high solids content and / or to improve rheological properties.

[0228] Polymers with functional microparticles, such as waterborne polyurethanes (WPU), polyester dispersions (PED), and polyacrylate emulsions (PAE), are commonly used in wood coatings, metal coatings, printing inks, architectural coatings, and plastic coatings. Despite the inherent advantages of polymers, they have some drawbacks such as low mechanical strength, low hardness, high water sensitivity, and thermal softening. Waterborne reactions have a relatively slow reaction rate and can also cause health hazards due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0229] In addition to making the polymer particles dispersible in a liquid, the surface functional groups eliminate slow reactivity and eliminate the need to use toxic chemicals to accelerate the reaction.

[0230] In the case of core and shell configuration, the nanomaterials present in the core and the crosslinkable functional groups on the shell help to protect the CNTs until secondary processing is performed. The released nanomaterials will increase the interaction and crosslinking density due to van der Waals forces.

[0231] As another aspect of the invention, the invention provides a microparticle composition consisting of nanomaterials, catalysts, crosslinking agents in the core, and functional groups on the shell. Other objects of the invention can be achieved by preparing microparticles with a particle size in the range of 0.01 microns to 10 microns and by modifying pre-existing microparticles.

[0232] Other objects of the invention can be achieved by preparing nanoparticles and microparticles with a particle size in the range of 0.01 microns to 100 microns, including modifying pre-existing microparticles.

[0233] The polymeric microparticles of the invention are designed to specific shapes, sizes, and surface chemistry, so that a mixture of organic and inorganic materials can be created.

[0234] Another aspect of the invention provides a method for manufacturing crosslinked polymeric microparticles with nanomaterials embedded in them. In addition, the crosslinked microparticles can be delivered in a masterbatch or as standalone particles.

[0235] Covalent adaptive networks (CANs) are a class of polymeric materials with covalent bonds that can break and recombine under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this way.

[0236] The low entropy of the functional groups on the microparticles increases the chances of CAN formation compared to conventional crosslinking agents. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional anchoring sites for CAN formation.

[0237] These cross-linkable reversible groups attached to the microparticles help create self-healing coatings, adhesives, composites, and structural materials through CAN.

[0238] The functional groups on the microparticles used in PSA (pressure sensitive adhesives) improve their tackiness, making them easier to adhere to surfaces. Functional microparticles provide additional contact points between the adhesive and the substrate, reducing the chance of creep failure over time.

[0239] The addition of nanomaterials (such as CNTs and graphene) with high modulus enhances resistance to deformation.

[0240] Pressure collapses the functional particles in the PSA, releasing chemicals, promoting further cross-linking with the substrate, and enhancing adhesion. Functional microparticles provide tunable bondline thickness. Microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0241] Another aspect of the invention relates to more efficient use of materials and achieving superior thermal and electrical conductivity by creating a pronounced honeycomb network at lower viscosity, resulting in the final polymer-based high conductivity product. BRIEF DESCRIPTION OF DRAWINGS

[0242] In the drawings, which are not necessarily drawn to scale, like numerals describe similar components throughout the several views. Like numerals having different letter suffixes can represent different instances of similar components. The drawings illustrate generally, by way of example, various aspects discussed in this document. In the drawings:

[0243] Figure 1 A schematic diagram depicting the method of the invention.

[0244] Figure 2A and Figure 2B Depict, respectively, currently available reaction injection molding methods, and the simplified method of the invention.

[0245] Figure 3A and Figure 3B Depict, respectively, currently available film lamination adhesives and the simplified method due to the invention.

[0246] Figure 4 Depict exemplary general structures of the matrix of the invention, as contemplated herein, and of the coated matrix.

[0247] Figure 5A and Figure 5B Depict exemplary compositional structures of the matrix of the invention, as contemplated herein.

[0248] Figure 6Exemplary matrices and coated matrices of the present invention as contemplated herein are depicted. The matrices can be coated on objects or located within coatings on various objects.

[0249] Figure 7 Scanning electron micrograph (SEM) images of exemplary hollow particles are depicted.

[0250] Figure 8 SEM images of exemplary hollow particles plus SPION plus copper are depicted.

[0251] Figure 9 SEM images of commercial PMMA (MX 500-ML, Soken) coated with carbon nanotubes (CNT) are depicted.

[0252] Figure 10 is a graph of heating profile using carbon nanostructure (CNS) susceptor.

[0253] Figure 11 is a graph showing selective placement of susceptor in shell on particles of the present invention.

[0254] Figure 12 is a graph showing sheet produced by non-covalent interaction.

[0255] Figure 13 is a schematic depicting functionalized CNT located in the shell of particles of the present invention.

[0256] Figure 14 is a graph showing post-functionalization of micro-particles for sequestering catalyst.

[0257] Figure 15 is a schematic showing use of micellar micro-particles to embed CNT and susceptor.

[0258] Figure 16 is a schematic showing micro-particles in micelles and catalyst embedding on CNT.

[0259] Figure 17 is a graph showing use of micellar micro-particles to sequester catalyst and embed susceptor.

[0260] Figure 18 is a core-shell particle generated using a commercial aqueous emulsion.

[0261] Figure 19 is a matrix particle (core) used as a carrier for delivery of CNT into different matrices.

[0262] Figure 20 is a graph of resistivity versus CNS loading showing resistivity from 1.0 x 1013 ohms to 6.0 x 10 3 ohms. DETAILED DESCRIPTION

[0263] Generally, and in one aspect, the present application relates to matrix particles comprising a matrix material as defined below, a susceptor, and a releasable ingredient. In some embodiments, the particles are in a core-shell configuration, or are just a core. The core is capable of changing its physical or chemical form, which allows the release of the releasable ingredient. When the particles are in a core-shell configuration, there can be one or more shells. The susceptor can be in the shell or in one or more shells. Similarly, the releasable ingredient can be in the shell or in one or more shells. The shell is thus a physically or chemically changeable material, such as an oligomer or a polymeric material. The presence of a susceptor in the matrix particles is optional. Such matrix particles are mixed in a physical or chemical composition of interest that needs to be physically or chemically affected by mixing with the matrix particles and applying an external force, such as radiofrequency or heat, which will change the matrix particles and release the releasable ingredient into the physical or chemical mixture or composition.

[0264] The present application relates generally to matrix microparticles and nanoparticles. While the application herein is discussed in terms of microparticles, it is equally applicable to nanoparticles.

[0265] a plurality of matrix particles, the plurality of matrix particles comprising matrix particle A and / or matrix particle B: wherein the matrix particle A comprises a core and optionally at least one shell, wherein the core comprises: (i) a matrix material, wherein the matrix material is capable of completely or partially changing its physical and / or chemical properties; (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material; and (iii) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the matrix material, wherein the at least one releasable ingredient is capable of physically or chemically affecting a bulk physical or chemically variable composition that is in contact with the plurality of matrix particles, and wherein the at least one shell comprises: (iv) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and (v) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the at least one shell, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemically variable composition that is in contact with the plurality of matrix particles;

[0266] and

[0267] wherein the matrix particle B comprises a core and optionally at least one shell, wherein the core comprises: (vi) a matrix material, wherein the matrix material is capable of completely or partially changing its physical and / or chemical properties; and (vii) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the matrix material, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles; and wherein the at least one shell comprises: (viii) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and (ix) the at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the at least one shell, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles; and wherein the at least one susceptor component and / or the releasable ingredient is capable of being activated by radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical attrition, or a combination thereof.

[0268] In one embodiment, the present application is directed to a plurality of matrix particles comprising a matrix particle A, wherein the matrix particle A comprises a core and optionally at least one shell, wherein the core comprises:

[0269] (i) a matrix material, wherein the matrix material is capable of completely or partially changing its physical and / or chemical properties;

[0270] (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material; and

[0271] (iii) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the matrix material, wherein the at least one releasable ingredient is capable of physically or chemically affecting a bulk physical or chemical variable composition in contact with the plurality of matrix particles, and wherein the at least one shell comprises:

[0272] (iv) optionally the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and

[0273] (v) at least one releasable ingredient, wherein the at least one releasable ingredient is embedded in the at least one shell, wherein the at least one releasable ingredient is capable of physically or chemically affecting the bulk physical or chemical variable composition in contact with the plurality of matrix particles; and

[0274] wherein the at least one susceptor component and / or the releasable ingredient is capable of being activated by radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical attrition, or a combination thereof.

[0275] In another embodiment, the present invention relates to a plurality of matrix particles, said plurality of matrix particles including matrix particle B, wherein said matrix particle B includes a core and optionally at least one shell, wherein said core comprises:

[0276] (vi) a matrix material, wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties; and

[0277] (vii) at least one releasable component, wherein the at least one releasable component is embedded in the matrix material, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles; and wherein the at least one shell comprises:

[0278] (viii) Optionally, the at least one receptor component, wherein the at least one receptor component is embedded in the at least one shell; and

[0279] (ix) the at least one releasable component, wherein the at least one releasable component is embedded in the at least one shell, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles; and wherein the at least one sensor component and / or the releasable component is capable of being activated by radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical abrasion, or a combination thereof.

[0280] In one embodiment, the present invention relates to a plurality of matrix particles, the plurality of matrix particles including matrix particle A and / or matrix particle B:

[0281] The matrix particle A includes a core and optionally at least one shell.

[0282] The core comprises:

[0283] (i) A matrix material, wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties;

[0284] (ii) at least one receptor component, wherein the at least one receptor component is embedded in the matrix material; and

[0285] (iii) at least one releasable component, wherein the at least one releasable component is embedded in the matrix material, wherein the at least one releasable component is capable of physically or chemically influencing the physical or chemical composition in contact with the plurality of matrix particles; and

[0286] The at least one shell comprises:

[0287] (iv) the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and

[0288] (v) at least one releasable component, wherein the at least one releasable component is embedded in the at least one shell, wherein the at least one releasable component is capable of physically or chemically affecting the physical or chemical composition in contact with the plurality of matrix particles;

[0289] and

[0290] wherein the matrix particle B comprises a core and optionally at least one shell, wherein the core comprises:

[0291] (vi) a matrix material, wherein the matrix material is capable of completely or partially changing its physical and / or chemical properties; and

[0292] (vii) at least one releasable component, wherein the at least one releasable component is embedded in the matrix material, wherein the at least one releasable component is capable of physically or chemically affecting the physical or chemical composition in contact with the plurality of matrix particles; and wherein the at least one shell comprises:

[0293] (viii) the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell; and

[0294] (ix) the at least one releasable component, wherein the at least one releasable component is embedded in the at least one shell, wherein the at least one releasable component is capable of physically or chemically affecting the physical or chemical composition in contact with the plurality of matrix particles; and wherein the at least one susceptor component or and / or the releasable and / or activatable component is capable of being activated by radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical attrition or a combination thereof.

[0295] In another embodiment, the above described matrix particles are contacted with or incorporated or dispersed in a chemical reaction mixture having constituent reactants that can undergo a chemical reaction, such as monomers or oligomers in a polymerization reaction. In another embodiment of the present application, the chemical reaction mixture having dispersed matrix particles is impinged with radio frequency electromagnetic radiation or microwave radiation, or is heated or mechanically attrited. The electromagnetic radiation (EMR) heats the susceptor component in the matrix particles. This heating in turn releases the active component, which then catalyzes the reaction in the reaction mixture. Thus, the reaction only begins when the RF or MW radiation releases the component from the matrix particles.

[0296] In another embodiment, the above-mentioned matrix particles are contacted with or incorporated or dispersed in a chemical mixture, wherein the components can or can not undergo a chemical change upon contacting the matrix particles, but undergo a physical change, such as a change in viscosity, upon release of the releasable and / or activatable ingredients via RF / MF radiation or heating or mechanical attrition.

[0297] Definitions

[0298] "Variable matrix" or "changing matrix" means that the matrix material within the matrix particles can be completely or partially deformed, dissolved, melted, expanded, contracted, ruptured, plasticized, or solvated. In other words, its physical and / or chemical form can be changed to make it susceptible to release of the active ingredients.

[0299] "Susceptor" means a particle within the matrix particles that is susceptible to heating or thermal activation by electromagnetic radiation, particularly radiofrequency and / or microwave.

[0300] "Affecting a chemical reaction" means that the releasable ingredients can activate or trigger, catalyze, co-catalyze, promote, accelerate, co-accelerate, inhibit, and / or heat a chemical reaction.

[0301] "Matrix material" or "matrix" means the base material in the matrix particles in which the susceptor components and / or the releasable and / or activatable ingredients are embedded. For example, the base material can be monomeric, oligomeric, or polymeric.

[0302] "Embedded" means that the susceptor or the releasable and / or activatable ingredients are encapsulated or entrapped within the matrix material, in intimate or associated contact with the matrix; for example, in pores of the matrix, or in association with one or more matrix materials, either within the matrix or on one or more surfaces of the matrix material, completely encapsulated within the matrix material, or partially embedded within the matrix particles by physical adhesion, or protruding from the surface portion of the matrix particles.

[0303] "Matrix particles" means nanometer or micrometer particles comprising a matrix material, a susceptor component, and a releasable and / or activatable ingredient, which are used to thermally activate the bulk reaction mixture described herein. In some embodiments, the susceptor component can be absent. In some embodiments, the susceptor itself can be the releasable and / or activatable ingredient.

[0304] "EM" means high frequency electromagnetic radiation, such as radiofrequency (RF) or microwave (MW).

[0305] "Releasable and / or activatable ingredient" refers to an ingredient contained within the matrix microparticle that, upon remote thermal activation of the susceptor within the matrix particle, functions to affect a chemical reaction, and then releases or activates the releasable and / or activatable ingredient. As an alternative to the term "releasable and / or activatable ingredient", the term "active ingredient" or "releasable ingredient" is used. In other words, the active ingredient embodies both its releasability characteristic as well as its activity characteristic. In many embodiments described hereinafter, the active ingredient is an active chemical ingredient.

[0306] "Bulk reaction mixture" refers to a reaction mixture that can be affected by the matrix particles in the release of the active ingredient. In the bulk reaction mixture, the matrix particles are dispersed, and then the susceptor is activated remotely to release the active ingredient, for example, catalyzing the bulk reaction mixture. As an example, the bulk reaction mixture can be a pre-polymerized material, even a post-polymerized material for increasing molecular weight, for example, any other chemical reaction, such as organic or inorganic, or a combined organic-inorganic reaction. The bulk reaction mixture can be transparent, translucent, or opaque. Or the bulk reaction mixture can change its transparency as the reaction proceeds.

[0307] "Pre-cursor" when used in the context of a reaction mixture refers to a reaction mixture that can evolve into an "intermediate" reaction mixture of a next form. In one embodiment, the pre-cursor reaction mixture can be monomeric, oligomeric, polymeric, or a mixture of one or more.

[0308] "Intermediate" when used in the context of a reaction mixture refers to a reaction mixture that results from a pre-cursor reaction mixture that has chemically and / or physically transformed into a next phase, and can further chemically and / or physically transform into a final phase of the reaction. In one embodiment, the intermediate reaction mixture can be monomeric, oligomeric, polymeric, or a mixture of one or more.

[0309] "Nucleus" refers to the portion of the matrix particle that contains the matrix material and in which the susceptor and / or the releasable ingredient is embedded.

[0310] "Shell" refers to the portion of the matrix particle that completely or partially covers the nucleus. It is made of a monomeric, oligomeric, or polymeric material, and can have the susceptor and / or the releasable ingredient embedded within it. The shell is changeable in that it can allow for the release of the releasable ingredient. In one embodiment, the shell can act as a force-improving material when the matrix particle is introduced into a chemical or physical mixture that requires a chemical and / or physical change. Subsequently, the shell can be changed by an external force when needed, for example, by RF, MF, mechanical shear, heating, or a combination of these techniques. In one embodiment, the shell is also made of a matrix material that is similar or different from the nucleus.

[0311] "Polymer brush-like particles" refer to particles having a dense layer of polymer chains attached to their surface, which resemble a brush in appearance.

[0312] "bulk physical or chemical composition" refers to a chemical composition that is understood in the art to have physical properties and chemical properties. The term "physical composition" can be used only to show that it can be subjected to a change in physical properties. As used herein, a chemical composition can be subjected to a change in at least one chemical property.

[0313] "physically or chemically affecting the bulk physical or chemical composition" refers to the incorporation of the matrix particles will change at least one physical property or one chemical property of the bulk. Or it will maintain one physical property or one chemical property that would change if the releasable ingredient was added without the matrix particle configuration of the present invention.

[0314] The precursors or intermediates can be converted by standard chemical or physical procedures and / or by RF and / or MW frequency shock as described in the present disclosure.

[0315] In another embodiment, the present invention relates to a method of incorporating matrix particles into a chemical reaction mixture to affect the chemical reaction. For example, the matrix particles can be dispersed in a monomer mixture prior to polymerization. In another embodiment, the present invention relates to activating a chemical reaction, such as a polymerization reaction, by high frequency electromagnetic radiation (EMR), such as radio frequency (RF) or microwave (MW) radiation heating susceptors in the matrix particles to activate the chemical reaction, for example, a polymerization reaction, and then release or activate the releasable and / or activatable ingredient. Alternatively, heat and mechanical abrasion (e.g., shear) can be used to release the releasable ingredient.

[0316] The present disclosure relates to materials and methods for conducting chemical reactions, such as polymerization reactions, where the chemical event is activated uniformly and on demand. The reactions as contemplated herein can be completed without the need to heat the entire block of reaction material; especially for highly packed blocks of material, opaque blocks of material, etc., without the limitation of penetration by light, such as infrared, ultraviolet, or visible light.

[0317] In some embodiments, the present invention relates to materials and methods for polymerization that do not require mixing of two reaction components, and in some embodiments are able to mix the two components but do not have an immediate or accelerated reaction and / or have a delayed reaction as desired. For example, some embodiments of the present disclosure provide low molecular weight and high performance materials for reducing the cure time in polymerization to minutes or hours and for reducing the cure time in mold manufacturing to a day or weeks. In one embodiment, the present invention can inhibit a chemical event by activating a chemical ingredient.

[0318] In some embodiments, the present disclosure provides materials and methods for polymerization that reduce or eliminate the need for higher molecular weight materials, where, for example, in injection molding and reaction injection molding, thus requiring high pressure as well as high temperature, and instead allow for increasing molecular weight during processing or within the mold and as needed. Preferably, the matrix particles have a low molecular weight matrix material. The low molecular weight matrix particles of the present invention provide for uniform mixing of fillers and provide for higher performance adhesion without undesirable rheological issues. The present invention allows for less complex equipment and cure on demand, which simplifies material preparation, storage, packaging, and handling.

[0319] The low molecular weight matrix particles provided by the present invention can be applied as adhesives to a variety of materials with a variety of applications. The present invention also provides for localized heating or thermal activation. The matrix particles as described herein provide for the ability to activate polymerization on demand. The polymerization as provided herein can be activated by the substrate, fillers, other additives, and the like. In other words, the opacity or lack of transparency of the bulk chemical mixture or the pore polymerization mixture does not significantly affect the reaction progress. The low molecular weight matrix particles as described herein provide for polymerization that is not dependent on total heating or thermal activation.

[0320] The low molecular weight materials of the present invention, i.e., the matrix particles, can be applied to a substrate in a pattern, thereby providing a patterned adhesive. Embodiments of the low molecular weight matrix particles of the present invention can be applied in a patterned manner, thereby providing a patterned adhesive that includes two-dimensional and three-dimensional selective activation.

[0321] In some embodiments, the matrix particles as described herein provide for polymerization for adhesives used in the production of converted goods, including rigid and or flexible laminates having two or more layers. In some embodiments, the matrix particles as described herein provide for polymerization for adhesives used in pressure sensitive materials and their related goods.

[0322] In one embodiment, the low molecular weight matrix particles of the present disclosure provide for improved curing of adhesives, coatings, and the like. This also includes substrates that enable the passage of energy, such as highly filled blocks of material, opaque blocks of material, and the like.

[0323] Embodiments of the present invention provide materials and methods for improved non-metallic molding, polymer molding, and high speed mold manufacturing and delivery.

[0324] The process can also occur at ambient conditions. Thermal activation for creating localized chemical events is achieved by the application of electromagnetic radiation (EMR), such as radio frequency (RF) radiation or microwave (MW) radiation. The present invention is applicable to bonding polymeric substrates, such as elastomers and rigid substrates, including fabrics and laminates.

[0325] For example, due to dissolution, melting, swelling, cracking, rupturing and / or otherwise deforming of a matrix of a heating susceptor component (such as carbon nanotubes) to release or activate a chemical component (such as a catalyst) which then catalyzes a reaction, for example a polymerization reaction or a reaction leading to a rapid energy generating reaction.

[0326] In another aspect, the present application relates to a matrix particle comprising:

[0327] (i) a matrix material, wherein the matrix material is capable of changing its physical and / or chemical properties completely or partially; and

[0328] (ii) at least one susceptor component, wherein the at least one susceptor component is embedded in the matrix material; and / or at least one releasable component embedded in the matrix material, wherein the at least one releasable component is capable of influencing a chemical reaction;

[0329] wherein the at least one susceptor component or and / or the releasable component is capable of being thermally activated by radio frequency (RF), microwave (MW) radiation, thermal activation or mechanical attrition.

[0330] In other words, in one embodiment, the matrix particle comprises a susceptor component or a releasable material or both. For example, a carbon nanostructure (such as a CNT or graphene) can act as a susceptor and be a releasable component.

[0331] In one embodiment, there is no susceptor component present because activation by RF or MF can or can not be required, because activation is thermally initiated or initiated via mechanical attrition.

[0332] In one embodiment, the matrix particle comprises a core, wherein the core itself acts as the matrix material. The core comprises a carbon nanostructure releasably attached to or embedded in or incorporated within the core. The core is made of an organic material, for example oligomeric or polymeric. For example, and as described elsewhere, the core is made of a wax.

[0333] In another embodiment, the matrix particle comprises a core and a shell. The core, the shell or the core and the shell is the matrix material. The matrix material comprises a carbon nanostructure releasably attached to, embedded in or incorporated within the matrix material. The core is made of an organic material, for example oligomeric or polymeric. For example, and as described elsewhere, the core is made of a wax. The organic material includes polymeric materials and oligomeric materials. The shell, if present, is made of an organic material such as an oligomeric or polymeric material which allows for deformation and release of the releasable component.

[0334] Nanometer and micrometer sized matrix particles can be used as carriers (see US Patent Application US 2023 / 0285948 Al to Malofsky et al., incorporated by reference in its entirety) for more efficient delivery of nanomaterials into sealants, coatings, composites, adhesives, and other polymeric products. Of particular interest is the achievement of physical properties of the final composition or physical product, including but not limited to thermal and electrical conductivity, improved or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy damping, and improved or controlled product life and failure.

[0335] The present invention relates to matrix particles containing nanomaterials, including metals and their chemical products, carbon nanostructures such as graphene and carbon nanotubes, which can improve physical, electrical, conductive, and simply provide greater amounts of the nanomaterials.

[0336] Optionally, crosslinking chemistry can be incorporated into or on the surface of the matrix particles by simply using surface chemistry, ligands, or oligomer-like structures capable of further enhancing the physical properties.

[0337] Specifically, incorporation or coating of polymer-based particles with nanomaterials such as carbon nanostructures such as carbon nanotubes or graphene can be performed. This basic concept is especially helpful in limiting the total amount of material required, providing a large surface area containing the structures, dispersing the separating forces through this large surface area, limiting agglomeration, etc. In the case of matrix particles coated with van der Waals and other physical or chemical force improving coatings, these effects can be further improved, amplified, controlled as needed.

[0338] In one aspect of the invention, the particles are coated with nanotubes, then coated with a force improving composition, incorporating more than one, and preferably three or more nanotubes, optionally followed by a force improving composition.

[0339] Optionally, any chemical functionalization can be incorporated within the particles or their coatings for subsequent reactions or physical effects. Examples of chemical reactions are myriad and are not limited, but include crosslinking and or polymerization reactions. Physical effects can include ligands, polymer or oligomer structures, for example by physically binding with the surrounding polymer matrix, or in the case of metallic or soapy ligands, emulsions, dispersions, etc. in solvents, water or other media. Optional inclusion of catalysts, co-catalysts, promoters, fuels, high energy materials, etc. are included in the invention.

[0340] It is another object of the present invention to provide polymer nanoparticles and microparticles with functional groups on the surface that can irreversibly / reversibly reduce when a composition containing polymer microparticles is applied to a composition containing sealants, composites, adhesives, other polymer products, and the like.

[0341] It is another object to provide functional groups that can non-covalently bond, such as hydrogen bonding or van der Waals forces, when a composition containing polymer microparticles is applied to a composition of sealants, composites, adhesives, and other polymer products.

[0342] In general, these functional nanoparticles and microparticles are a versatile platform with tunable properties that can be tailored to meet specific application requirements. These functional nanoparticles and microparticles can be used in many applications, including adhesives, composites, laminates, sealants, coatings, inks, plastics, and the like in many end products in many consumer, industrial, and or medical applications.

[0343] Functional microparticles containing reactive functional groups, such as carboxylic acid, amino groups, thiols, epoxide, acrylic, isocyanate, can crosslink with other functionalized particles.

[0344] Polymers with functional microparticles, such as waterborne polyurethane (WPU), polyester dispersion (PED), and polyacrylate emulsion (PAE), are commonly used in wood coatings, metal coatings, printing inks, architectural coatings, and plastic coatings. Despite the inherent advantages of the polymers, they have some disadvantages, such as low mechanical strength, low hardness, high water sensitivity, and thermal softening. Waterborne reactions have a relatively slow reaction rate and can also cause health hazards due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0345] In addition to making the polymer particles dispersible in a liquid, the surface functional groups eliminate slow reactivity and eliminate the need to use toxic chemicals to speed up the reaction.

[0346] In the case of core and shell configuration, the nanomaterials present in the core and the crosslinkable functional groups on the shell help to protect the CNTs until secondary processing is done. The released nanomaterials will increase the interaction and crosslinking density due to van der Waals forces.

[0347] As another aspect of the present invention, the present invention provides a microparticle composition comprising nanomaterials, catalysts, crosslinking agents in the core, and functional groups on the shell. Other objects of the present invention can be achieved by preparing microparticles with a particle size in the range of 0.01 microns to 10 microns and by modifying pre-existing microparticles.

[0348] Other objects of the present invention can be achieved by preparing nanoparticles and microparticles with a particle size in the range of 0.01 microns to 100 microns, including modifying pre-existing microparticles.

[0349] The polymeric microparticles of the present invention are designed with specific shape, size, and surface chemistry, so that a mixture of organic and inorganic materials can be created.

[0350] Another aspect of the present invention provides a method for manufacturing cross-linked polymeric microparticles with nanomaterials embedded in them. Furthermore, the cross-linked microparticles can be delivered in a masterbatch or as standalone particles.

[0351] Covalent adaptable networks (CANs) are a class of polymeric materials with covalent bonds that can break and recombine under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this way.

[0352] The low entropy of the functional groups on the microparticles increases the chance of CAN formation compared to conventional cross-linkers. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional anchoring sites for CAN formation.

[0353] These cross-linkable reversible groups attached to the microparticles help create self-healing coatings, adhesives, composites, and structural materials through CAN.

[0354] The functional groups on the microparticles used in PSAs (pressure sensitive adhesives) improve their tackiness, making them easier to adhere to surfaces. The functional microparticles provide additional contact points between the adhesive and the substrate, reducing the chance of creep failure over time.

[0355] The addition of nanomaterials with high modulus such as CNTs and graphene enhances resistance to deformation.

[0356] Pressure causes the functional particles to collapse in the PSA, releasing chemicals, promoting further cross-linking with the substrate, and enhancing adhesion. The functional microparticles provide tunable bondline thickness. The microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0357] Another aspect of the present invention relates to more efficient use of materials and achieving superior thermal and electrical conductivity by creating a pronounced honeycomb network at lower viscosity, resulting in the final polymer-based high conductivity product.

[0358] The ability to heat the composition on demand and with low to no significant additional energy input and release catalysts, co-catalysts, promoters or such other reaction initiating compounds enables new methods, materials and subsequent products and methods previously unattainable, especially with regard to hot melt adhesives, molding, preforms, plastics for thermoplastic molding and overmolding of different materials. In overmolding processes, the adhesive layer acts to compatibilize thermoplastic and thermoset plastics.

[0359] In particular, the present invention is directed to the addition of carbonaceous susceptor particles coated with a material capable of preventing strong van der Waals interactions and or single or clustered carbonaceous susceptors coated with a material capable of preventing van der Waals interactions such that the latter's force effects are significantly minimized or eliminated, thereby allowing the easy addition of said material, especially at higher concentrations, to facilitate RF heating for easy physical deformation, including softening or melting. The above coating significantly reduces clumping or other macrostructures capable of causing significant viscosity increases or similar physical effects. The coating can slow, stop or prevent the desired thermal conduction, electrical conduction or other similar effects. The above compositions can be easily mixed into existing formulations using conventional equipment.

[0360] Hot melt adhesive applications illustrate the general possible effects extendable to other products containing materials ranging from low molecular weight materials, biologically sourced, temperature sensitive renewable materials to high molecular thermoplastic resins and polymers.

[0361] In particular, carbonaceous materials can be coated as individual, clustered, coated particles and optionally incorporated into other combinations of materials such that van der Waals effects are minimized, thereby significantly reducing viscosity in temperature ranges allowing more of the coated material to be incorporated.

[0362] In one embodiment, the present invention allows for higher loadings of the material to facilitate RF heating, particularly microwave heating to facilitate ease of processing and or high levels of reinforcement. As described in the above background section, other purposes can include thermal or electrical conductivity, reaction initiation, matching CTE, thermal conductivity via the particles, etc.

[0363] Preforms include another exemplary application set where we can first add the carbonaceous material to the polymer in the melt for any of the properties described above or for the reactive option using particles containing catalysts and the like as described in U.S. Patent Application 18 / 055,302 to Malofsky et al., especially to initiate reactions where the particles remain intact at the shaping or deforming temperature during the part manufacturing process until RF heating to even higher temperatures for catalyst or otherwise release or exposure and subsequent activation. RF heating will enable high throughput and lower cost high speed manufacturing. In certain applications, this approach can eliminate B-stage preforms or material refrigeration.

[0364] Plastic injection molding, blow molding, and hot-bonding layers of polymer or polymer coatings (extrusion) function similarly to the above.

[0365] The benefits of added reinforcement materials such as carbon, glass, aramid, ultra-high molecular weight polyethylene, and natural and synthetic fibers and other combinations are demonstrated in a variety of ways.

[0366] The approach provides the benefits of ease of addition and lower viscosity.

[0367] Examples of applications include reinforced hot melt adhesives; reactive hot melt adhesives; continuous or discontinuous hot melt coated articles, webs, films; continuous or discontinuous hot melt coated fibers; hot melt adhesive articles including fibers, ropes, shapes, dots, and preform articles made from monomers, polymers, and / or oligomers.

[0368] One of the benefits is the ability to perform substrate attachment with minimal extrusion of adhesive material.

[0369] Polymer energy minimization and fine polymerization control

[0370] In one embodiment, the present invention also relates to minimizing the energy required to activate chemical reactions and their effects, especially avoiding limited energy penetration with total heating, for example, with UV light, and the ability to activate one or more chemical events on demand, in whatever order or series is required to achieve the desired result.

[0371] Activation of chemical properties and polymerisation through opaque objects

[0372] Uncontrolled, rapid reactions in UV curing chemistry can result in highly crosslinked systems. In some applications where toughness is desired, uncontrolled UV curing reactions result in undesirable vitrification and brittleness. Embodiments of the present invention provide for uniform distribution of the catalyst / co-catalyst as a component of the matrix particles in the reaction mixture. Without being bound by theory, this uniform distribution in the reaction mixture enables the initiation of the polymerization reaction at multiple sites simultaneously, which contributes to the creation of a uniform polymer network. Without being bound by theory, the simultaneous reaction at multiple sites results in controlled exotherm and improved efficiency.

[0373] Embodiments of the present invention provide for the activation of the polymerization catalyst at one or more depths on the matrix material. The catalyst can be on the surface of the matrix material, or at a depth below the surface, or embedded within the matrix material. For example, the catalyst can be located at a depth of up to about 0.01 pm, about 0.01 pm to about 0.05 pm, about 0.05 pm to about 0.1 pm, about 0.1 pm to about 0.2 pm, about 0.2 pm to about 0.3 pm, about 0.3 pm to about 0.4 pm, about 0.4 pm to about 0.5 pm, about 0.5 pm to about 0.6 pm, about 0.6 pm to about 0.7 pm, about 0.7 pm to about 0.8 pm, about 0.8 pm to about 0.9 pm, about 0.9 pm to about 1 pm, about 1 pm to about 5 pm, about 5 pm to about 10 pm, or greater than about 10 pm, and any and all increments therebetween.

[0374] In one embodiment, the present invention relates to solid state polymerization, where the molecular weight increases over time, where the polymer has been in a solid or high viscosity state, but can increase the polymerization yield or molecular weight, for example, in situ, with the inclusion of matrix microparticles and treatment with RF or MW.

[0375] Particle composition and structure

[0376] Reference is now made to Figure 5A and Figure 5B In some embodiments, the matrix particles of the present invention can have a highly variable composition. The matrix material can optionally be deformable. In some embodiments, a plurality of matrices are used in one embodiment. In some embodiments, one or more susceptor components can be used. In some embodiments, one or more releasable and / or activatable ingredients are included within or on the matrix. In some embodiments, the one or more releasable and / or activatable ingredients include one or more of a catalyst, a co-catalyst, a co-reactant, a fuel, an explosive, another ingredient, and mixtures thereof. In some embodiments, the releasable and / or activatable ingredients are released by one or more means, including, for example, dissolution, swelling, cracking, light, and / or one or more combinations thereof.

[0377] Variable matrix material

[0378] As used herein, a "variable matrix" refers to a material that, when heated, can deform, dissolve, melt, fracture, expand, shrink, plasticize, and / or solvate in a manner that releases its active components (e.g., chemical contents). Matrix particles can have virtually any geometry, shape, or size. For example, such as... Figure 4 As shown, the matrix particles can be formed into shapes including one or more of the following: spheres, sheets, strips, plates or coatings, rods or expanded fibers, porous structures including, for example, foams, or one or more irregular or amorphous shapes.

[0379] In some implementation schemes, such as Figure 5A and Figure 5B As shown, the matrix material is continuous. In some embodiments, the matrix material has an isotropic structure. In some embodiments, the matrix material is discontinuous. In some embodiments, the matrix material has an anisotropic or orthotropic structure. In some embodiments, the matrix material is a mixture of one or more materials or structures. In some embodiments, the matrix material comprises a mixture of isotropic and anisotropic structures.

[0380] The matrix material can be composed of any suitable material understood in the art. In some embodiments, the matrix material can be monomeric, oligomeric, or polymeric. For example, the matrix can contain methyl methacrylate. In some embodiments, the matrix material consists of polymer microparticles. For example, the polymer microparticles can be made of polymethyl methacrylate (PMMA), styrene, and / or one or more polymers or copolymers thereof. The microparticles can also be blends, alloys, and mixtures of polymers.

[0381] Polymer microparticles can include polymer microspheres and microcapsules. Microcapsules can be porous or partially open.

[0382] In some embodiments, the microparticles are spherical microparticles. The microparticles can have an effective diameter of about 0.1 pm to about 1000 pm. As used herein, "effective diameter" refers to the diameter of an equivalent spherical microparticle of the same volume or weight. For example, the microparticles can have an effective diameter of about 0.1 pm to about 0.5 pm, about 0.5 pm to about 1 pm, about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 50 pm, about 50 pm to about 100 pm, about 100 pm to about 200 pm, about 200 pm to about 300 pm, about 300 pm to about 400 pm, about 400 pm to about 500 pm, about 500 pm to about 600 pm, about 600 pm to about 700 pm, about 700 pm to about 800 pm, about 800 pm to about 900 pm, about 900 pm to about 1000 pm, and any and all increments therebetween.

[0383] In one embodiment, the microparticles have an effective diameter that is one of the following values measured in pm, or one of the values in the range defined by any two of the following values in pm (including the end points):

[0384] 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, and 1,000.

[0385] In one embodiment, microspheres as referred to herein are microparticles composed of a uniform and solid polymeric matrix material, while microcapsules are core-shell microparticles, where the core can be solid, liquid or even a hollow space. Microparticles can also be prepared as porous matrix materials composed of interconnected microspheres. The porous matrix material can include pores formed on the surface or external and / or internal formed pores. The pores can be isolated or interconnected. The pores result in a very low mass density matrix material. The pores are suitable for entrapping sensates and releasable and / or activatable ingredients, such as activators, catalysts, co-catalysts, co-reactants, oxidizing agents, reaction inhibitors, accelerators, and / or one or more other releasable ingredients.

[0386] In some embodiments, the matrix material consists of monodisperse polymer particles. In some embodiments, the matrix material consists of polydisperse polymer particles. Polydispersity can include narrow dispersity of particle size, such as a monomodal distribution, a bimodal distribution, or a trimodal distribution. In some embodiments, polydispersity includes moderate dispersity of particle size. In some embodiments, polydispersity includes wide dispersity of particle size. In some embodiments, polydispersity includes particle sizes in the range of about 1 nm to about 10 nm, about 10 nm to about 50 nm, about 50 nm to about 100 nm, about 100 nm to about 200 nm, about 200 nm to about 400 nm, about 400 nm to about 600 nm, about 600 nm to about 800 nm, about 800 nm to about 1000 nm, about 1 pm, about 1 pm to about 1.5 pm, about 1.5 pm to about 2 pm, about 2 pm to about 2.5 pm, about 2.5 pm to about 3 pm, about 3 pm to about 3.5 pm, about 3.5 pm to about 4 pm, about 4 pm to about 4.5 pm, about 4.5 pm to about 5 pm, and any and all increments therebetween. In some embodiments, the average particle size is at most about 0.1 pm. In some embodiments, the average particle size is in the range of about 0.1 pm to about 0.5 pm, about 0.5 pm to about 0.8 pm, about 0.8 pm to about 1 pm, about 1 pm to about 1.2 pm, about 1.2 pm to about 1.5 pm, about 1.5 pm to about 1.8 pm, about 1.8 pm to about 2 pm, about 2 pm to about 4 pm, about 4 pm to about 6 pm, about 6 pm to about 8 pm, about 8 pm to about 10 pm, about 10 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 60 pm, about 60 pm to about 80 pm, about 80 pm to about 100 pm, about 100 pm to about 200 pm, about 200 pm to about 400 pm, about 400 pm to about 600 pm, about 600 pm to about 800 pm, about 800 pm to about 1000 pm, and any and all values therebetween.

[0387] In some embodiments, the matrix material in the matrix particles has a molecular weight of at most 10 kDa. In some embodiments, the matrix material in the matrix particles has a molecular weight of about 10 kDa to about 25 kDa, about 25 kDa to about 50 kDa, about 50 kDa to about 75 kDa, about 75 kDa to about 100 kDa, about 100 kDa to about 125 kDa, about 125 kDa to about 150 kDa, about 150 kDa to about 175 kDa, about 175 kDa to about 200 kDa, about 200 kDa to about 225 kDa, about 225 kDa to about 250 kDa, and any and all increments therebetween. Matrix materials having much higher molecular weights, such as matrix materials of branched or cross-linked polymers such as rubbers, are also within the scope of the present application.

[0388] In some embodiments, the matrix material has a molecular weight provided by a value in kDa of any of the following or a range (including the endpoints of the range) provided by a value in kDa of any two of the following:

[0389] 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, and 1000000.

[0390] In some embodiments, the dispersion of polymeric particles includes particles having a low cross-linking level. In some embodiments, the dispersion of polymeric particles includes particles having a standard or intermediate cross-linking level. In some embodiments, the dispersion of polymeric particles includes particles having a high cross-linking level.

[0391] Susceptor

[0392] In some embodiments, the matrix particle composition of the present disclosure comprises one or more susceptor. A susceptor as contemplated herein is a particle that can be heated or otherwise activated to generate heat. The susceptor is composed of a material that produces a higher heating rate or lower heat capacity than the surrounding or adjacent matrix material. The higher heating rate of the susceptor results in a change in the matrix as previously defined upon application of an energy source without bulk heating of the matrix material. The heated susceptor can induce a deformation of the matrix material such that components or chemical ingredients of the reaction, such as a catalyst or inhibitor within the matrix, can participate in one or more chemical reactions. Embodiments of susceptors that can be heated include one or more carbon-based or silicon carbide-based materials. The susceptor can include one or more ferrous or non-ferrous metals, including, for example, one or more transition metal oxides, ferrites, and / or one or more combinations thereof. Transition metals include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.

[0393] Embodiments of the iron susceptor include one or more of iron oxide powders, superparamagnetic iron oxide (SPION) particles, and the like, including one or more combinations thereof. Embodiments of the susceptor include one or more of graphene, graphene oxide fullerenes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, carbon sheets, buckypaper, nanocrystalline cellulose, and the like, including one or more combinations thereof.

[0394] Embodiments of the susceptor are composed of one or more materials that generate heat upon exposure to radio frequency (RF) radiation and / or microwave (MW) radiation; hereinafter, microwave heating is used as an example to describe the method of the present application. Externally applied microwaves can generate heat internally. Without being bound by theory, unlike conventional bulk heating methods, the rate of microwave-induced heating is not limited by the rate of heat transfer from an external heat source to the interior of the bulk reaction mixture. Thus, microwave heating is more efficient than conventional heating. That is, microwave heating provides faster and more uniform heating of the bulk reaction mixture having the susceptor particles of the present application dispersed into the bulk reaction mixture. Moreover, conventional heating occurs via heat flow from an external heat source, while conventional heating propagates from the surface to the core of the bulk reaction mixture by one or more means, including conduction and / or convection, as well as through and mixing.

[0395] Thus, the surface of the bulk reaction mixture typically remains at a higher temperature than the core of the bulk reaction mixture. For example, the outer surface of the reaction vessel in direct contact with the bulk reaction mixture will heat the immediate area of the bulk reaction mixture, with a gradual decrease in temperature to the core. Even if an equilibrium temperature is established, the wall of the bulk reaction mixture proximate to the reaction vessel will likely have a much higher temperature, resulting in non-uniform yield and chemistry of the bulk reaction mixture progressing to the final product. For example, in a polymerization reaction, starting with monomers and oligomers and if temperature dependent, the bulk reaction mixture will have a molecular weight distribution from the outside to the core of the bulk reaction mixture, or will have more degradation closer to the reaction vessel, or will have more gelling / crosslinking at the reaction vessel wall.

[0396] This can result in non-uniform heating, overheating, and / or underheating, resulting in reaction non-uniformity, which can affect yield or create problems with other reaction parameters. However, because microwave heating can occur uniformly whether at the core or outside of the bulk reaction material, because microwaves penetrate the susceptor material almost instantaneously and heat activate or excite the susceptor within the core of the bulk material, it generates heat inside the bulk material, allowing the core of the susceptor to remain at even higher temperatures than the surface, in general. That is, very small local sources of heating can be produced.

[0397] Accordingly, in some embodiments, the susceptor is located within the core of the substrate particle (such as a polymeric substrate material), so that when microwaves are applied, the susceptor is heated, causing heating of the core of the substrate particle. In some embodiments, the susceptor is located on the surface of the substrate particle, so that when microwaves are applied, causing localised sharp heating of the surface of the substrate particle.

[0398] Embodiments of the susceptor can be activated at one or more frequencies or frequency ranges. The frequencies can include one or more frequencies in the following ranges: up to about 100 MHz, about 100 MHz to about 200 MHz, about 200 MHz to about 400 MHz, about 400 MHz to about 600 MHz, about 600 MHz to about 800 MHz, about 800 MHz to about 1000 MHz, about 1000 MHz to about 1500 MHz, about 1500 MHz to about 2000 MHz, about 2000 MHz to about 2500 MHz, about 2500 MHz to about 5000 MHz, about 5000 MHz to about 7500 MHz, and any and all increments therebetween. A preferred frequency range is 900 MHz to 2500 MHz.

[0399] In some embodiments, the frequency is one of the following values measured in MHz, or is in a range defined by any two of the following values measured in MHz (including the end points of such ranges):

[0400] 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 35, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, and 7500.

[0401] Embodiments of the susceptor include one or more shapes. For example, the susceptor can be spherical, cylindrical, disc-like, tubular, or cuboidal, and can have one or more other regular polygonal prismatic shapes, one or more irregular shapes, and / or one or more combinations thereof.

[0402] In some embodiments, the susceptor is functionalized. In some embodiments, the susceptor includes both functionalized and non-functionalized susceptor. In some embodiments, the functional group includes a surface functional group, where the functional group is added by one or more monomer or polymer surfactants. For example, in some embodiments, the susceptor can include one or more carboxyl groups, hydroxyl groups, methyl groups, etc. The susceptor can include one or more functional groups that increase or decrease hydrophilicity or hydrophobicity. The susceptor can include different functional groups such that regions of the susceptor are more hydrophilic or hydrophobic than other regions of the susceptor. For example, the susceptor can have a functional group such that the susceptor has a polar end and a non-polar end.

[0403] Releasable and / or activatable ingredients

[0404] In some embodiments, the matrix material includes one or more releasable and / or activatable ingredients, also referred to as releasable ingredients or active ingredients. The one or more releasable and / or activatable ingredients can be encapsulated or embedded within the matrix material, which can be polymeric or oligomeric or monomeric or a mixture of the three. For example, the one or more releasable ingredients can be physically embedded or encapsulated within one or more pores of the microparticle matrix material. In some embodiments, the one or more releasable ingredients can be chemically embedded within the polymeric matrix material. That is, the one or more releasable ingredients can be chemically bonded to one or more materials of the matrix within the matrix particle. The releasable ingredients can include one or more catalysts, co-catalysts, co-reactants, oxidizing agents, reaction-inhibiting compounds, chelating agents, initiators, promoters, activators (including surface activators), modifiers, fuels, explosives, and / or one or more combinations thereof. As understood in the art, the releasable ingredients can include any chemical, combination of chemicals, organic or inorganic chemical. In some embodiments, the one or more releasable ingredients can include one or more compounds capable of initiating polymerization (e.g., anionic, cationic, or free radical polymerization).

[0405] In some embodiments, the one or more releasable ingredients include one or more ingredients that initiate one or more reactions, including redox reactions, such as in anaerobic adhesion. For example, the one or more releasable ingredients can include one or more of a hydroperoxide and one or more transition metals. The one or more releasable ingredients can be contained within different microcapsules within the matrix, within different pores, embedded within the matrix material, bound to one or more components of the matrix material, or otherwise kept separate and only contact when the matrix material is heated or activated.

[0406] In one embodiment, the one or more releasable ingredients include one or more of a metal promoter or catalyst, such as ferrocene or other metallocene. The one or more catalysts can be combined with peroxides and / or other compounds to activate or deactivate polymerization. In some embodiments, the catalyst includes one or more of copper acetylacetonate, copper 2-ethylhexanoate, ferrocene, dimethylaminomethyl ferrocene, and / or one or more combinations thereof. In some embodiments, the one or more releasable ingredients include one or more radical stabilizers, such as hydroquinone or p-methoxyphenol.

[0407] In some embodiments, including for example compositions that include anionic cyanoacrylate and / or methylene malonate, the one or more releasable ingredients can include one or more inorganic or organic bases (e.g., sodium propionate). In yet another example, for cationic polymerization of epoxy resins, one or more ingredients are released, such as diaryliodonium and triarylsulfonium, a blocked super acid, a cationic catalyst. In some embodiments, such as in polycondensation, the one or more releasable ingredients can include one or more catalysts, such as antimony, germanium, titanium, and aluminum compounds.

[0408] Fuel and explosives, among others, are another example where such materials can be used. Specifically, fuel or other explosive materials can be utilized, alone or in combination, with or without additional materials as described, to initiate chemical action reactions, to release large amounts of energy in various forms, alone or in combination with other reactive materials, to facilitate events, for example, from powering a piston in an engine, to explosive devices, to combustion events, to simple high speed heating events.

[0409] In one embodiment, the releasable ingredients can change the physical properties of the bulk reaction mixture, for example, increase or decrease its viscosity, or provide color or other optical properties to the bulk reaction mixture, for example, especially once it reaches its chemical equilibrium with the product.

[0410] It should be noted that the carbon nanostructures simultaneously act as a susceptor and / or a releasable ingredient. In other words, in one embodiment, the carbon nanostructures are present only as a susceptor. In another embodiment of the present application, the nanostructures are present as a releasable and / or activatable ingredient. In yet another embodiment, the carbon nanostructures are present and act as both a susceptor and a releasable and / or activatable ingredient. Embodiments of releasable agents include one or more of graphene, fullerenes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, carbon sheets, buckypaper, and the like, including one or more combinations thereof. In one embodiment, the releasable ingredient is a carbon nanotube releasably attached to the core, shell, deformable material, force- improving material, or matrix material of the matrix particle. In another embodiment, the number of carbon nanotubes attached at a given location in a cluster within the matrix particle is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0411] Particle structure

[0412] Embodiments of the present disclosure provide matrix particle compositions having a matrix material that includes one or more particles as described herein, one or more susceptors as described herein, and / or one or more releasable ingredients as described herein. The matrix particle compositions can simply be configured as a matrix material that contains susceptors and releasable ingredients as described above, and can exist in any geometric configuration as required for the application. For example, the matrix particles can exist in a spherical or approximately spherical configuration, a ribbon or sheet-like configuration, a rod or fiber-like configuration, a porous configuration (including, for example, a foam), and / or one or more irregular configurations. It should be noted that in some embodiments, the releasable ingredients can not be physically released, but can be chemically activated to perform their function.

[0413] In some embodiments, the matrix particle compositions can have a distinct phase that contains susceptors and / or activatable and / or releasable ingredients. In some embodiments, the matrix particle compositions can have a continuous phase that contains both susceptors and / or releasable ingredients. In some embodiments, one or more susceptors or releasable ingredients, such as an activator / catalyst, can be included in a first layer and / or one or more subsequent or alternating coatings of the matrix material in the matrix particle composition.

[0414] In some embodiments, the particulate composition comprises a hydrophilic chemical, a hydrophobic chemical, and / or one or more regions having both hydrophilic and / or hydrophobic chemicals. In some embodiments, one or more functionalized receptors are located within or on the particulate composition such that receptor organelles with the same charge are aligned with the particulate chemical. For example, the hydrophilic regions of one or more receptors are aligned with one or more regions of the matrix particulate composition having one or more hydrophilic chemicals. Similarly, in some embodiments, the hydrophobic regions of one or more receptors are aligned with one or more regions of the matrix particulate composition having one or more hydrophobic chemicals. Thus, the location of one or more receptors within or on the matrix particulate composition can be guided by the hydrophilic or hydrophobic regions of the matrix particulate composition.

[0415] Embodiments of the matrix particle composition include configurations in which a receptor is combined with one or more of a matrix material and a releasable component. Embodiments of the matrix particle composition include configurations in which the receptor may be present on the surface of a first matrix material or in another matrix material in contact with the first matrix material. In some embodiments, the particle composition includes a first matrix material layer and one or more additional adjacent matrix material layers. For example, in some embodiments, the matrix particle composition may include a single matrix material or matrix material layers, two matrix material layers, three matrix material layers, etc. The matrix particle composition may include one or more homogeneous layers, one or more heterogeneous layers, and / or combinations thereof. For example, in some embodiments, a matrix particle composition may contain more than one receptor or more types of receptors. Additional receptors may be located in the same matrix material layer, adjacent matrix material layers, alternating matrix material layers, etc.

[0416] In some embodiments, more than one releasable component, such as an activator or catalyst, is included in the same matrix material layer or different matrix material layers. The activator or catalyst may be located in the same matrix material layer, adjacent matrix material layers, or alternating matrix material layers.

[0417] In some embodiments, each layer of matrix material includes one combination of susceptor, activator / catalyst, and releasable ingredient (such as an activator / catalyst). In some embodiments, each layer of matrix material includes more than one combination of susceptor and releasable ingredient (such as an activator / catalyst). In some embodiments, the matrix particle composition includes more than one layer of matrix material, wherein each layer of matrix material includes the same combination of susceptor and releasable ingredient (such as an activator / catalyst). In some embodiments, the particle composition includes more than one layer of matrix material, wherein each layer of matrix material includes a different combination of susceptor and releasable ingredient (such as an activator / catalyst).

[0418] In some embodiments, the matrix particle composition includes more than one layer of matrix material, wherein each layer is formulated to have a curing time within the same time interval. In some embodiments, the matrix particle composition includes more than one layer of matrix material, wherein each layer is formulated to have a curing time with a different time interval, such as in a molded structure. In some embodiments, the layered matrix materials are sequenced to control stress and or other physical properties in the particle composition or in the material into which or onto which it is applied. For example, in some embodiments, the particle composition is formulated with different amounts or concentrations of one or more activatable matrix components, activators, catalysts, releasable ingredients, etc.

[0419] The matrix particles can be optionally all or partially supported and or otherwise protected by, for example, crushable or non-crushable carriers including, for example, metals, ceramics, or glasses, etc., and in three dimensions such as foams, solid objects coated or impregnated with the matrix particle composition. Even further, for example, the objects can have rough, sharp, or similar surface textures to, for example, prevent crushing with matrix material placed below but surrounding the structure. Another example can include the matrix particle composition as coated beads, granules, fines, etc., including metal glass beads or even the susceptor as a bead to melt or otherwise deform the matrix particle composition coated on a surface by heating.

[0420] In some embodiments, multiple matrices are used if, for example, a particular application requires multiple matrices. The matrices can be formed in various configurations including one or more coatings, patterned films or layers, textured geometries, etc.

[0421] In all applications, the susceptor is excited via external high frequency electromagnetic radiation (EMR) to partially or fully alter (e.g., deform or dissolve or melt) one or more surrounding matrices to release catalysts, co-catalysts, inhibitors, co-reactants or promoters, fuels, explosives, or other ingredients. In some embodiments, the susceptor (such as a CNT) is excited or activated to heat or thermally activate the matrix. In some embodiments, heating or thermally activating the matrix deforms the matrix material.

[0422] Matrix particles provide an efficient way to deliver the susceptor into formulations used, for example, in adhesives, coatings, composites, molding applications, and polymer systems. Using matrix particles as a carrier helps to maintain rheological properties, for example, CNTs can cause viscosity spikes even at low loadings, creating processing challenges.

[0423] Depending on the particular application, various susceptors are also used. For example, in curing opaque polymers, single- and multi-walled carbon nanotubes, sheets, and fiber susceptors often provide very effective energy susceptor materials for heating and releasing a given catalyst. In other examples where optical transparency is a driving factor, CNTs with boron nitride can be used for transparency.

[0424] The size of the susceptor component ranges from the nanometer range to the micrometer to the millimeter. For example, in some embodiments, the size of the susceptor component ranges from 1 nm to 10 nm, from about 10 nm to about 100 nm, from about 100 nm to about 1 µm, from about 1 µm to about 10 µm, from about 10 µm to about 100 µm, from about 100 µm to about 1000 µm, and any and all increments therebetween.

[0425] In some embodiments, the size of the susceptor component is one of the following values measured in nm, or is within a range defined by any two of the following values in nm (including the endpoints of such ranges), or is the sum of any two values in nm:

[0426] 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, and 1000000.

[0427] In some embodiments, the susceptor is uniformly dispersed in the matrix material. The dispersion of the susceptor can allow for the use of an optimized weight of the susceptor. In some embodiments, a well-dispersed susceptor can create a strong van der Waals force between the susceptor and the matrix material, which is theorized, without wishing to be bound by any theory, as a limitation on the scope of the present invention. The interaction of the susceptor and the matrix can also be achieved through covalent and non-covalent bonding.

[0428] The susceptor component can include carbon nanotubes, carbon nanostructures, ferrite particles including superparamagnetic iron oxide nanoparticles (SPIONs), and the like.

[0429] The catalyst, promoter, inhibitor, co-reactant, accelerant, fuel, explosive, other ingredients, and mixtures can in fact be any composition, but preferably where the final particles are present in a concentration suitable for the desired chemical property. The application can be very unique and its requirements can vary widely.

[0430] In some embodiments, the susceptor component concentration can generally vary from 0.01% to as much as 10% depending on the application itself and the requirements of its final arbiter. The energy requirements are derived from the deformation temperature and kinetics, heat transfer to the surrounding matrix, time frame of the event (from a thousandth of a second to tens of seconds or more). In some embodiments, the matrix includes one or more waxes. The wax can include one or more natural waxes, such as carnauba wax. The wax can include one or more synthetic waxes, such as, for example, polyethylene wax. The wax can include a combination of both synthetic and natural waxes such that the combination has a well-defined melting point. In some embodiments, the wax has a melting and / or deformation temperature in the range of about 50°C to 300°C. For example, in some embodiments, the wax matrix has a melting temperature of about 50°C to about 75°C, about 75°C to about 100°C, about 100°C to about 125°C, about 125°C to about 150°C, about 150°C to about 175°C, about 175°C to about 200°C, about 200°C to about 225°C, about 225°C to about 250°C, about 250°C to about 275°C, about 275°C to about 300°C, and any and all increments therebetween.

[0431] Waxes as matrix materials

[0432] "Wax" refers to any naturally occurring or synthetically occurring wax. It also includes a blend or mixture of one or more naturally occurring and / or synthetically occurring waxes. Naturally occurring waxes include plant-based waxes, animal waxes, and mineral waxes. Synthetic waxes are made by physical or chemical means. Because they are mixtures, naturally occurring waxes are softer than pure components and melt at lower temperatures.

[0433] The wax can be a paraffin wax, which is a hydrocarbon with the general formula C n H2n+2 straight-chain alkanes, where n varies from 13 to 80. The paraffin defined by n = 13 is called tridecane, and the paraffin with n = 80 is called octadecane. C 13 The melting point of the wax is -5.4°C. Similarly, the melting point of C60 wax is 100°C. Similarly, the melting point of higher waxes (C60 to C80) is higher than 100°C. Depending on the temperature range to which the bulk reaction mixture needs to be heated, the wax-based matrix particles with a particular wax core that changes, deforms, or melts at that particular temperature range can be customized.

[0434] Examples of plant-based waxes include mixtures of unesterified hydrocarbons, which can predominate over esters. The cuticular waxes of plants are mixtures of substituted long-chain aliphatic hydrocarbons, which contain alkane, alkyl esters, sterol esters, fatty acids, primary and secondary alcohols, diols, ketones, aldehydes, aliphatic aldehydes, primary and secondary alcohols, beta-diketones, triacylglycerols, and the like. Specific examples of plant waxes include carnauba wax, candelilla wax, copernicia wax, jojoba plant wax, bayberry wax, Japan wax, sunflower wax, tall oil, beef tallow wax, rice bran wax, and beef tallow.

[0435] Animal waxes include beeswax and waxes secreted by other insects. The main component of beeswax used to construct beehives is palmitic acid myricyl ester, which is an ester of a triacontanol and palmitic acid. Whale wax is found in large quantities in the head oil of sperm whales. One of its main components is cetyl palmitate, which is another ester of a fatty acid and a fatty alcohol. Lanolin is a wax obtained from sheep wool, which consists of esters of sterols. Examples of other animal waxes include wool wax, shellac, and ozocerite.

[0436] Examples of mineral waxes include montan wax, paraffin wax, microcrystalline wax, and intermediate wax. Although many natural waxes contain esters, paraffin wax is a hydrocarbon, usually a mixture of alkanes of a homologous series of chain lengths. Paraffin wax is a mixture of saturated normal and isoalkanes, naphthenes, and alkyl- and naphthenic-substituted aromatics. The degree of branching has an important influence on performance. Montan wax is a petrochemical wax extracted from coal and lignite. It is very hard, reflecting a high concentration of saturated fatty acids / esters and alcohols. Montan wax includes chemical components formed from long-chain alkyl acids and alkyl esters with chain lengths of about 24 to 30 carbons. In addition, natural montan includes resin acids, polyterpenes, and some alcohols, ketones, and other hydrocarbons, making it not a “pure” wax. The saponification value of montan, which is a saponifiable wax, is about 92, and its melting point is about 80°C. In addition to montan wax, other natural sources of wax are known to be used in various industries, and include petroleum waxes derived from processed crude oil, which include macrocrystalline wax, microcrystalline wax, petrolatum, and paraffin wax. Paraffin wax is also a natural wax derived from petroleum and is formed primarily of straight-chain alkanes with an average chain length of 20-30 carbon atoms.

[0437] Synthetic waxes include those based on polypropylene, polyethylene, and polytetrafluoroethylene. Other synthetic waxes are based on fatty acid amines, Fischer-Tropsch, and polyamides. Polyethylene and related derivatives are also used. Some waxes are obtained by pyrolyzing polyethylene at 400°C. The products have the formula (CH2). n H2, where n is in the range of approximately 50 to 100.

[0438] Synthetic waxes are also known, including low molecular weight (i.e., molecular weight less than about 10,000) synthetic polyethylene waxes, and polyethylene with waxy properties. These waxes can be formed by the direct polymerization of ethylene under conditions suitable for controlling the molecular weight. Polyethylene with a molecular weight in the range of about 2,000-4,000 is a wax, and when the molecular weight is in the range of about 4,000-12,000, it becomes a wax resin.

[0439] Fischer-Tropsch waxes are polymethylene waxes produced through specific polymerization synthesis, particularly Fischer-Tropsch synthesis (polymerizing carbon monoxide under high pressure, high temperature, and special catalysts to produce hydrocarbons, followed by distillation to separate the product into liquid fuels and waxes). These waxes (microcrystalline, polyethylene, and polymethylene hydrocarbon waxes) can be chemically modified, for example, by air oxidation (to obtain an acid value of 30 or lower and a saponification value not lower than 25) or modified with maleic anhydride or carboxylic acid. These modified waxes are more readily emulsified in water and can be saponified or esterified. Other known synthetic waxes are polymerized α-olefins. These are waxes formed from higher α-olefins with 20 or more carbon atoms and waxy properties. These materials are highly branched, have a wide molecular weight distribution, and melting points in the range of about 54°C to 75°C, as well as molecular weights of about 2,600 to 2,800. Therefore, waxes vary depending on the properties of the base material, the polymerization or synthesis method, and the resulting chemical structure (including the use and type of any chemical modification).

[0440] Matrix particles can be prepared through processes such as polymerization or physical material decomposition, emulsion polymerization, dispersion polymerization and / or suspension polymerization, core-shell polymerization, solvent dispersion, cavitation of fluids and / or solids in fluids, merging of sensors and catalysts, pulverization after merging, and grinding.

[0441] like Figure 1 As shown, solid matrix particles contain carbon nanotubes as sensor components and a catalyst for accelerating a chemical reaction. Radio frequency (RF) shocks are applied to the matrix particles, heating the carbon nanotube particles. These particles are embedded near the catalyst particles. The matrix material melts or deforms completely or partially, but due to the RF, the catalyst is released, subsequently catalyzing the reaction of the material incorporating multiple matrix particles.

[0442] In this embodiment, the RF or MW energy only heats and melts the matrix particles. The heating rate of the matrix particles is many orders of magnitude higher than the adjacent material. The differential heating of the matrix particles results in deformation of the matrix particles without causing bulk heating. In addition, the uniform dispersion of the matrix particles and the size of the particles does not result in significant heating of the adjacent formulation. Thus, the RF or MW energy activates the release of the contents of the matrix particles to uniformly and rapidly induce polymerization. In one embodiment, it requires 2% or less of a catalyst, typically in the ppm range. In one embodiment, the percentage of catalyst is any value selected from the values provided below, or in a range defined by any two of the values below, including the endpoints of the range:

[0443] 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

[0444] Figure 2 shows reaction injection molding as currently practiced and the present invention. As a result of the present invention, complex mixing is not required. Instead of thermal curing, RF curing is performed. This eliminates or reduces the use of steel molds; the reaction can be completed at lower pressure without the application of total heat, and the reaction is faster. It also significantly reduces the cure time.

[0445] As shown in Figure 3, as currently practiced, for film lamination adhesives, multiple film lines are used for multiple layers. By using the present invention, one line can be used for multiple layers. The advantages are high speed, no heating, opaque materials can be cured, and there is no depth limitation. Control of the location of the cure is achieved in addition to strict control of when the cure is performed in production.

[0446] In one embodiment, the RF or MW is a directed source, as the radiation is focused on a specific object or area of interest.

[0447] In some embodiments, the matrix can have a coating. In some embodiments, the coating is continuous. In some embodiments, the coating is discontinuous. In some embodiments, the coating is patterned. In some embodiments, the coating is deposited in one or more layers. In some embodiments, the coating is anisotropic.

[0448] In some embodiments, the coating is attached to the matrix by one or more means, including, for example, entanglement, van der Waals interactions, through one or more chemically bound compounds, etc. In some embodiments, the coating comprises one or more of a wax, one or more hydrophobic compounds and / or hydrophobic functional groups, one or more compounds having a non-polar component including a non-polar tail (including one or more oils), a fatty acid, etc.

[0449] The coating can have a thickness of up to 10 nm, about 10 nm to about 15 nm, about 50 nm to about 100 nm, about 100 nm to about 500 nm, about 500 nm to about 1 pm, about 1 pm to about 2 pm, about 2 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 50 pm, about 50 pm to about 100 pm, about 100 pm to about 500 pm, about 500 pm to about 1 mm, about 1 mm to about 2 mm, about 2 mm to about 5 mm, about 5 mm to about 10 mm, about 10 mm to about 50 mm, about 50 mm to about 100 mm, about 100 mm to about 500 mm, and any and all increments therebetween.

[0450] Embodiments of the matrix can include one or more additional components for providing controlled on-demand release. For example, the matrix and or a coating containing the matrix and or a discontinuous coating is coated or uncoated on any surface susceptible to activation of the matrix, such as round fibers, textile fibers, polymeric fibers, hollow fibers, reinforcing fibers such as those used in composites, sheeting, flexible or inflexible materials, foams and other porous structures, nonwoven materials, woven materials, polymeric scrims, reinforcing scrims, and the like.

[0451] In some embodiments, the matrix includes one or more fillers. Embodiments of the fillers include particles, such as fibers. The fibers can have one or more lengths. The fibers can include milled fibers. Embodiments of the fillers include one or more of clays, aggregates, plasticizers, plastic particles, nanoparticles of different shapes, and the like.

[0452] Particle activation methods and apparatus

[0453] The particle activation, methods, and apparatuses constitute a complete "system" including various types of susceptors, activators, matrix components, RF and / or MW energy sources, material handling, software, and controls.

[0454] Speed, time, unit throughput, form factor, topology, and unit volume are all relevant characteristics of the system that are analyzed and adjusted for each application to produce the desired end product or result for a given set of materials.

[0455] Susceptors are excited via external high frequency EMR to partially or fully deform one or more surrounding matrices to release catalysts, co-catalysts, co-reactants, or accelerators. In the realm of remote Joule heating properties such as CNTs, without being bound by theory of the physical properties of how CNTs heat surrounding materials, heated CNTs are used to deform surrounding matrices.

[0456] In the most common form, microwave electromagnetic radiation having a wavelength in the range of about one meter to one millimeter; and a frequency of 300 MHz (1 m) to 300 GHz (1 mm) is used to excite the susceptor and deform the surrounding matrix to release the catalyst or activator material. In practice, a variety of electromagnetic wavelengths and frequencies can be used; preferably, the most common frequencies currently for consumer and industrial applications are 915 MHz and 2450 MHz. However, one or more suitable frequencies can include up to about 100 MHz, about 100 MHz to about 200 MHz, about 200 MHz to about 400 MHz, about 400 MHz to about 600 MHz, about 600 MHz to about 800 MHz, about 800 MHz to about 1 GHz, about 1 GHz to about 1.5 GHz, about 1.5 GHz to about 2 GHz, about 2 GHz to about 2.5 GHz, about 2.5 GHz to about 5 GHz, about 5 GHz to about 7.5 GHz, and any and all increments therebetween.

[0457] Table 1: Radiation frequencies and wavelengths

[0458] Microwave frequencies Wavelengths 245 MHz ± 0.2% 122.19 cm 433.92 MHz ± 0.2% 69.14 cm 580 MHz ± 0.2% 51.61 cm 915 MHz ± 13 MHz 32.75 cm 2.45 GHz ± 50 MHz 12.24 cm 5.8 GHz ± 75 MHz 5.17 cm 24.125 GHz ± 125 MHz 1.24 cm

[0459] In one embodiment of the present application, the process of applying electromagnetic radiation, i.e., impinging the bulk reaction mixture, is carried out for a period of time of from 10 seconds to 60 minutes. In another embodiment, the radiation time is any one of the following values in seconds, or a value within a range defined by any two of the following values in seconds (including the endpoints of the range):

[0460] 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, and 3600.

[0461] In one embodiment of the present application, the EMR is used as a beam to impinge the bulk reaction mixture, wherein the bulk reaction mixture is immersed in the RF or MW radiation.

[0462] Applications

[0463] Exemplary applications include, but are not limited to, the following:

[0464] Adhesive bonding

[0465] On-demand release of catalysts, co-catalysts, and / or accelerators, where limitations such as total heating, multi-component mixing, long polymerization times, and / or depth limitations (e.g., the use of light and / or surface primer activation systems) can be eliminated by dispersing the components in the polymerizable composition as needed and activating them on demand at the required moments during the bonding or adhesion and / or component preparation process. Benefits also include more precise targeting without altering the viscosity kinetics of the reaction.

[0466] Coating

[0467] On-demand release of catalysts, co-catalysts, and / or accelerators, where limitations such as total heating, multi-component mixing, long polymerization times, and / or depth limitations (e.g., the use of light and / or surface primers to activate systems) can be eliminated by dispersing the components in the polymerizable composition as needed and activating them on demand at the desired time during coating or part preparation. Benefits also include flow control before and without altering viscosity kinetics in the event of a reaction. Limitations of UV-curable systems, such as incomplete curing in shaded areas and parts with complex shapes, can be overcome. There are no limitations on curing, 3D, and concave parts with large attachments. Coating rates can be matched to upstream and downstream processing, eliminating bottlenecks in manufacturing throughput.

[0468] Moulding and composites

[0469] Catalysts, co-catalysts, and / or accelerators are released on demand, where limitations such as total heating, multi-component mixing, long polymerization times, and / or depth limitations (e.g., the use of light and / or surface primer activation systems) can be eliminated by dispersing the components in the polymerizable composition as needed and activating them on demand at the desired time during molding or die and / or part preparation. The part can be filled with a variety of materials. The cross-section of the part can be equal to or greater than 14 feet × 14 feet. In the context of this specification, unless otherwise stated, all publications, patent applications, patents, and other references mentioned herein are expressly incorporated herein by reference in their entirety for all purposes as if fully explained.

[0470] Surprisingly, nanoparticles and microparticles have been found to serve as carriers for more effectively delivering nanomaterials into sealants, coatings, composites, adhesives, and other polymer products. Of particular interest are the realization of physical properties of the final composition and / or physical product, including but not limited to thermal and electrical conductivity, improved and / or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy damping, and improved or controlled product lifespan and / or failure.

[0471] The present invention specifically, but not exclusively, carries particles that are layered with nanomaterials, filled with nanomaterials or otherwise filled with nanomaterials, including metals and their chemical products, graphene, nanotubes and similar structures, to benefit from improved physical, electrical, conductive and other similar properties, to thereby, for example, minimize the need for more significant amounts of the nanomaterials.

[0472] Optionally, cross-linking chemistry can be incorporated into or on the surface of the particles simply using surface chemistry or as ligands or oligomer-like structures that can even further enhance the physical properties.

[0473] Specifically, incorporation and or coating of polymer-based particles can be carried out within the polymer-based particles that contain nanomaterials, such as nanotubes or similar structures, especially, for example, carbon nanotubes and or graphene or similar structures. This basic concept is especially helpful to limit the total amount of material needed, can provide a large surface area containing the structures, through which dispersion forces are dispersed, agglomeration is limited, etc. In the case of nanoparticles and or microparticle coating with improved coatings of van der Waals forces and other physical or chemical forces, these effects can be further improved and or amplified and controlled as needed.

[0474] The literature documents coating of the particles with, for example, carbon nanotubes or coating of individual nanotubes. Here, we distinguish by coating the particles with nanotubes and then coating with force-improving compositions, incorporating more than one and preferably three or more nanotubes and or then coating with force-improving compositions.

[0475] Optionally, if any chemical functionalization is used for subsequent reactions or physical effects, it can be incorporated into the particles and or their coatings. Examples of chemical reactions are myriad and are not limited, but include cross-linking and or polymerization reactions. Physical effects can include ligands, polymer and or oligomer structures, for example, physically bound to the surrounding polymer matrix, or in the case of metal or soap-like ligands, emulsions, dispersions, etc. in solvents, water or other media. Optionally included - see U.S. Patent Application 18 / 055,302 to Malofsky et al., incorporated by reference as if fully set forth herein - catalysts, co-catalysts, promoters, fuels, high-energy materials, etc. are included in the invention.

[0476] Another object of the present invention is to provide polymer nanoparticles and microparticles with functional groups on the surface that can irreversibly / reversibly reduce when compositions containing polymer microparticles are applied to compositions containing sealants, composites, adhesives, other polymer products, etc.

[0477] Another object is to provide functional groups capable of non-covalent bonding, such as hydrogen bonding or van der Waals forces, when the composition containing the polymeric microparticles is applied in compositions of sealants, composites, adhesives, and other polymeric products.

[0478] Generally, these functional nanoparticles and microparticles are a versatile platform with tunable properties that can be tailored to meet specific application requirements. These functional nanoparticles and microparticles can be used in many applications, including but not limited to adhesives, composites, laminates, sealants, coatings, inks, plastics, etc. in many end products in many consumer, industrial, and or medical applications.

[0479] Functional nanomicro particles include latex particles, nanogel and microgel particles, colloidal particles, including but not limited to colloidal particles composed of polymer chains dispersed in water or other solvents. Also included are microgel particles that can swell or shrink in response to changes in their environment.

[0480] Functional microparticles containing reactive functional groups, such as carboxylic acid, amino groups, thiols, epoxide, acrylic, isocyanate, can be crosslinked with other functionalized particles.

[0481] In coatings, crosslinked polymeric microparticles are used to produce compositions containing high solid content and / or to improve rheological properties.

[0482] Polymers with functional microparticles, such as waterborne polyurethane (WPU), polyester dispersion (PED), and polyacrylate emulsion (PAE), are commonly used in wood coatings, metal coatings, printing inks, architectural coatings, and plastic coatings. Despite the inherent advantages of polymers, they have some drawbacks, such as low mechanical strength, low hardness, high water sensitivity, and thermal softening. Waterborne reactions have a relatively slow reaction rate and can also cause health hazards due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0483] In addition to making the polymeric particles dispersible in liquids, the surface functional groups eliminate slow reactivity and eliminate the need to use toxic chemicals to speed up the reaction.

[0484] In the case of core and shell configuration, the nanomaterials present in the core and the crosslinkable functional groups on the shell help to protect the CNTs until secondary processing is performed. The released nanomaterials will increase the interaction and crosslinking density due to van der Waals forces.

[0485] As another aspect of the invention, the invention provides a microparticle composition consisting of nanomaterials, catalysts, crosslinkers in the core, and functional groups on the shell. Other objects of the invention can be achieved by making microparticles with a particle size in the range of 0.01 microns to 10 microns and by modifying pre-existing microparticles.

[0486] Other objects of the invention can be achieved by making nanoparticles and microparticles with a particle size in the range of 0.01 microns to 100 microns, including modifying pre-existing microparticles.

[0487] The polymeric microparticles of the invention are designed to specific shapes, sizes, and surface chemistries, so that a mixture of organic and inorganic materials can be created.

[0488] Another aspect of the invention provides a method for making crosslinked polymeric microparticles with nanomaterials embedded in them. In addition, the crosslinked microparticles can be delivered in a masterbatch or as standalone particles.

[0489] Covalent adaptable networks (CANs) are a class of polymeric materials with covalent bonds that can break and recombine under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this way.

[0490] The low entropy of the functional groups on the microparticles increases the chance of CAN formation compared to conventional crosslinkers. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional anchoring sites for CAN formation.

[0491] These crosslinkable reversible groups attached to the microparticles help create self-healing coatings, adhesives, composites, and structural materials through CAN.

[0492] The functional groups on the microparticles used in PSAs (pressure sensitive adhesives) improve their tackiness, making them easier to adhere to surfaces. The functional microparticles provide additional contact points between the adhesive and the substrate, reducing the chance of creep failure over time.

[0493] The addition of nanomaterials with high modulus such as CNTs and graphene enhances resistance to deformation.

[0494] Pressure causes the functional particles to collapse in the PSA, releasing chemicals, promoting further crosslinking with the substrate, and enhancing adhesion. The functional microparticles provide a tunable thickness of the adhesive layer. The microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0495] Another aspect of the invention relates to more efficient use of materials and achieving superior thermal and electrical conductivity by creating a pronounced honeycomb network at lower viscosity to bind them, thereby obtaining the final polymer-based highly conductive product.

[0496] The ability to heat the composition on demand and at low to no significant additional energy input and release catalysts, co-catalysts, promoters or such other reaction initiating compounds enables new methods, materials and subsequent products and methods to be achieved that were previously unattainable, especially with regard to hot melt adhesives, molding, preforms, plastics for thermoplastic molding and overmolding of different materials. In overmolding processes, the adhesive layer acts to compatibilize thermoplastic and thermoset plastics.

[0497] In particular, the invention relates to the addition of carbonaceous susceptor particles coated with a material capable of preventing strong van der Waals interactions and or single or clustered carbonaceous susceptors coated with a material capable of preventing van der Waals interactions such that the latter's force influence is significantly minimized or eliminated, thereby allowing the easy addition of said material, especially at higher concentrations, to facilitate RF heating for easy physical deformation, including softening or melting. The above coating significantly reduces clumping or other macrostructures that can cause significant viscosity increases or similar physical effects. The coating can slow, stop or prevent the desired thermal conduction, electrical conduction or other similar effects. The above composition can be easily mixed into existing formulations using conventional equipment.

[0498] Hot melt adhesive applications illustrate the general possible effects that can be extended to other products containing materials ranging from low molecular weight materials, biologically sourced, temperature sensitive renewable materials to high molecular thermoplastic resins and polymers.

[0499] In particular, the carbonaceous material can be coated as individual, clustered, coated particles and optionally incorporated into other combinations of materials such that the van der Waals effects are minimized, thereby significantly reducing the viscosity in a temperature range that allows more of the coated material to be incorporated.

[0500] In one embodiment, the invention allows for higher loadings of the material to facilitate RF heating, particularly microwave heating to facilitate ease of processing and or high levels of reinforcement. As described in the above background section, other purposes can include thermal or electrical conductivity, reaction initiation, matching CTE, thermal conductivity via the particles, etc.

[0501] Preforms include another exemplary application set where we can first add the carbonaceous material to the polymer in the melt for any of the properties described above or for the reactive option using particles containing catalysts and the like as described in US Patent Application 18 / 055,302 to Malofsky et al., especially to initiate reactions where the particles remain intact at the forming or deforming temperature during the part manufacturing process until RF heating to even higher temperatures for catalyst or otherwise release or exposure and subsequent activation. The RF heating will enable high throughput and lower cost high speed manufacturing. In certain applications, this approach can eliminate B-stage preforms or material refrigeration.

[0502] Plastic injection molding, blow molding, and hot-bonding layers (extrusion) of polymers or polymer coatings act similarly as described above.

[0503] The benefits of added reinforcement materials such as carbon, glass, aramid, ultra-high molecular weight polyethylene, and natural and synthetic fibers and other combinations are demonstrated in a variety of ways.

[0504] The approach provides the benefits of ease of addition and lower viscosity.

[0505] Examples of applications include reinforced hot melt adhesives; reactive hot melt adhesives; continuous or discontinuous hot melt coated articles, webs, films; continuous or discontinuous hot melt coated fibers; hot melt adhesive articles including fibers, ropes, shapes, dots, and preform articles made from monomers, polymers, and / or oligomers.

[0506] One of the benefits is the attachment of substrates with minimal extrusion of adhesive material.

[0507] Some uses of the invention include the following: • Conductive materials • Thermally conductive materials • Recyclable materials • Architectural, industrial coatings • Sealants - strength, durability, and adhesion of sealants. Improved elasticity and flexibility. Resistance to UV radiation and moisture, better adhesion • Composites - fracture toughness, high modulus • Adhesives - fracture toughness, high modulus • Pressure sensitive adhesives • Pressure sensitive reactive adhesives • Drug delivery - these particles can also be designed to release drugs in a controlled manner, allowing for targeted drug delivery and reducing the risk of side effects. • Imaging - contrast agents for imaging techniques such as MRI and CT scans. • 3D printing: higher Z-direction properties - • Coating - Abrasion Resistance • Plywood • Geotextiles (for road construction, railway construction, and riverbank construction) • Roofing, insulation and cladding, acoustic and structural laminates

[0508] Examples of end or intermediate products

[0509] Examples of final or intermediate products include the following: • Additives in coatings are used to provide various properties such as scratch resistance, UV protection, and water resistance. • Automotive coatings, used to improve their durability. • Textile coatings are used to provide a variety of properties, such as water resistance, stain resistance and antimicrobial activity. • Porous ceramic materials with specific pore sizes and distributions. The polymer template is removed during firing, leaving behind porous ceramic materials with customized properties. • Shoes – lining, main body components, and their final construction. • Clothing – linings, main body parts, etc., and their final construction. • Packaging – linings, main components, etc., as well as their final construction, sealing, and closure. • Box – lining, main body, etc., and their final construction. • Decorative flexible and laminated products (tablecloths, curtains, etc.). •furniture. • Oil and air film products.

[0510] 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 pertains. In the event of any conflict, this specification (including the definitions) shall prevail.

[0511] Unless otherwise specified, trademarks are displayed in capital letters.

[0512] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight.

[0513] Unless otherwise stated, pressure expressed in psi will be gauge pressure, and pressure expressed in kPa will be absolute pressure. However, pressure differences are expressed as absolute values ​​(e.g., pressure 1 is 25 psi higher than pressure 2).

[0514] When equivalent, concentration, or other values or parameters are given as a range or list of upper and lower values, this is to be understood as the disclosure of all ranges formed by any pair of any upper value and any lower value, regardless of whether ranges are separately disclosed. Where a range of values is recited in the art, unless otherwise stated, the range is intended to include the end points thereof and all integers and fractions within that range. The ranges of the present disclosure are not intended to be limited to the specifically enumerated values.

[0515] When the term“about” is used, it is intended to mean an effect or result that can be achieved within a certain tolerance, and the skilled person knows how to achieve that tolerance. When the term“about” is used to describe an end point of a value or range, the disclosure is to be understood to include the specific value or end point mentioned.

[0516] 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.

[0517] The transitional phrase“consisting of’ excludes any element, step, or ingredient not specified in the claim, thereby limiting the claim to the listed materials only. When the phrase“consisting of’ appears in the clause of the claim following the transitional phrase“comprising,” the recitation that the claim is drawn to a composition rather than an article of manufacture is clarified by the transitional phrase.

[0518] 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 application. “Consisting essentially of’ claims occupy a middle ground between closed-ended claims written in the“consisting of’ format and completely open-ended claims drafted in the“comprising” format. Optional additives, as defined herein, at levels suitable for such additives, and minor impurities are not excluded from the composition by the term“consisting essentially of’.

[0519] Also, the use of“or” and“and / or” means include, rather than exclude, unless the context is expressly to the contrary. For example, a condition A or B, or A and / or B, is satisfied by anyone 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).

[0520] 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 and at least one and the singular as also including the plural, unless it is obvious that it is meant otherwise.

[0521] All references cited in this document are incorporated by reference as if fully set forth herein. Experimental examples

[0522] Example 1 - methylene malonate polymerisation via anionic polymerisation

[0523] Composition

[0524] This embodiment relates to a curable composition containing matrix particles, the curable composition comprising: (a) a methylene malonate monomer, (b) a stabilizer solution, and (c) an activator, (i) wherein the activator comprises a cation at a level of 0.1 ppm to 500 ppm; and (ii) wherein the activator is encapsulated in a heat deformable and or heat soluble matrix particle that also contains an RF susceptor (e.g. carbon nanostructures).

[0525] Formulation

[0526] The formulation is made as follows in weight % with other variations added as needed: 1. 20% to 70.0% of a difunctional or higher methylene malonate monomer, oligomer or resin; 2. 20% to 70% of a malonic acid diethyl ester, malonic acid dipropyl ester, malonic acid dibenzyl ester, malonic acid diisobornyl ester or similar methylene malonate monomer; and 3. 0.1% to 0.7% of an acid stabilizer solution.

[0527] For the above formulation, the 50 nanometers to 5000 nanometers matrix particles comprise 90% paraffin or olefin polymer or oligomeric wax or similar, 8% carbon nanotubes and 2% activator such that the particles exhibit 5 ppm of activator cations in the final overall composition.

[0528] Matrix studies

[0529] In summary, the activator ranges from 0.5 ppm to 500 ppm, which is achieved by varying the concentration of the substrate particles from 0.5% to 10% and the power level to determine the appropriate frequency, power level in the application itself, thus determining the time required to activate the particles and thus the time required for polymerization.

[0530] MF - transparent filler

[0531] The formulation produced as above can then be adjusted by using a chemically neutral, optionally dry, RF transparent filler, such as a mineral (such as calcium carbonate), glass or glass powder, polymer powder, wood or other organic powder, silica, silicates, and ceramics. In cases where moisture is a challenge, a combination of transition metal accelerators can be used, specifically copper hexanoate and iron, specifically ferrocene.

[0532] Curing, substrates and containers

[0533] As the formulation changes, so does the speed of cure and thus the exotherm of polymerization. Therefore, one should start with a small amount of formulation placed so that a thin film is placed between two slides, thus minimizing the material and still creating anaerobic conditions and allowing for observation. In the next step, spacers can be added to create a thick adhesive layer. In the next step, one can move to narrow test tubes and or syringe bodies. Next, one can scale up to larger test tubes and or syringe bodies. Next, one can scale up to small beakers. Larger volume material assemblies and or vessels can be placed in oil and / or water to control the heat conduction of the exotherm to avoid dangerous situations.

[0534] In essence, the RF transparent material is desired for the container or a portion of the container so that the required RF energy can be properly transmitted.

[0535] Example 2 - radical polymerisation via anaerobic polymerisation

[0536] Composition

[0537] This embodiment relates to a curable composition comprising: (a) acrylate and or methacrylate monomers, (b) a hydroperoxide or perester initiator, and (c) an activator, (i) wherein the activator comprises a copper ion source at a copper level of 0.1 ppm - 100 ppm; (ii) wherein the activator is encapsulated in a heat deformable and or heat dissolvable substrate particle that also contains an RF susceptor.

[0538] Formulation

[0539] Formulations are made as follows in % by weight, with other variations as needed: 1. 20% to 70.0% triethylene glycol dimethacrylate, polyurethane diacrylate or epoxy diacrylate 2. 20% to 70% lauryl methacrylate, ethyl methacrylate, methyl methacrylate, ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate 3. 0.5% to 3.0% cumene hydroperoxide 4. 0.3% to 0.7% stabilizer solution 5. 0.1% to 0.5% saccharin

[0540] To these formulations are added 50 nanometer to 5000 nanometer matrix particles comprising one or more of 90% by weight of paraffin wax, an olefin polymer, an oligomeric wax or similar matrix; 8% carbon nanotubes; and 2% copper ethylhexanoate activator. These components are added so that the particles exhibit 0.6 ppm copper in the final composition.

[0541] Instead of 2% copper, 0.06% copper can also be added to the formulation of 50% particle dispersion containing 2% ferrocene in the particles.

[0542] Matrix studies :

[0543] The copper ethylhexanoate concentration ranges from 0.6 ppm to 60 ppm, achieved by varying the concentration of matrix particles, varying the % of compound in the matrix particles from 0.5% to 10% and varying the power level to determine the appropriate RF wavelength, power level in the application itself, and thus the time required to activate the particles and thus the time required for polymerization.

[0544] RF - transparent filler

[0545] The formulations produced as above are adjusted by using chemically neutral, optionally dry, RF transparent fillers such as many minerals (such as calcium carbonate), glass or glass powder, polymer powder, wood or other organic powder, silica, silicates, ceramics, etc. In cases where moisture is a challenge, a combination of transition metal accelerators is used, in particular copper ethylhexanoate and iron, specifically ferrocene.

[0546] Curing, substrates and containers

[0547] As the formulation changes, the speed of cure and thus the exotherm of polymerization also changes. Therefore, first place a small amount of the formulation so that a thin film is placed between two slides thus minimizing the material and still creating anaerobic conditions and allowing for observation. Next, add spacers to create a thick adhesive layer. Next, scale up to a narrow test tube and or syringe body. Next scale up to a larger test tube and or syringe body. Next scale up to a small beaker. Place larger volume assemblies and or containers in oil and or water to control the heat transfer of the exotherm to avoid dangerous situations. In essence, RF transparent material is desired for the container or a portion of the container so that the required RF energy can be properly transmitted.

[0548] Example 3 - method using commercial microparticles as core

[0549] This study demonstrates the use of available microparticles as a core of the matrix particle to carry the activator to initiate the cure in a one-component adhesive formulation. The main objective of this study is to demonstrate the use of commercial PMMA already on micrometer / nanometer scale particles as a carrier for acrylic activation by attaching copper activator to the surface of the core of commercially available particles.

[0550] Table 2: Commercially available particles tested

[0551] PMMA product name Particle size MX-500ML 0.8 pm to 30 pm; average particle size: 5 pm MP-1441 0.15 pm to 0.4 pm; average particle size: 0.17 pm XX-6666Z Average particle size 4.7 pm MX-180TA 0.8 pm to 30 pm; average particle 1.8 pm

[0552] **The MX-500ML, MP-1441, MX-180TA are sourced from Soken, Japan and XX6666Z is sourced from Sekisui kasei, Japan.

[0553] The following formulations were prepared to evaluate the conditions to prepare matrix particles using various commercially available PMMA particles as a core of the matrix particle.

[0554] Formulation 1 - Commercial PMMA (MX-500ML) (2g) was first filter washed with 10% (100 mL) sodium hydroxide solution, then filter washed with 10% (10 mL) copper chloride solution, rinsed with deionized water, and dried.

[0555] Formulation 2 - Commercial PMMA (MX-500ML) (2g) was first filter washed with 10% (100 mL) sodium hydroxide solution, then filter washed with 10% (10 mL) copper chloride solution, rinsed with deionized water, and dried.

[0556] Formulation 3 - Commercial PMMA (MP-1441) (2g) was filter washed with 10% (100 mL) sodium hydroxide solution, then filter washed with 10% (10 mL) copper chloride solution, rinsed with deionized water, and dried.

[0557] Preparation 4 - Commercial PMMA (XX-6666Z) (2 g) was filtered washed with 10% (100 mL) sodium hydroxide solution, then filtered washed with 10% (10 mL) copper chloride solution, rinsed with deionized water, and dried.

[0558] Preparation 5 - Commercial PMMA (MP-1441) (5 g) was sonicated with a solution of copper (II) 2-ethylhexanoate (1 g) in isopropyl alcohol and filtered washed with additional isopropyl alcohol.

[0559] Preparation 6 - Commercial PMMA (MX-180TA) (2 g) was sonicated with a solution of copper chloride (0.125 g) in isopropyl alcohol and filtered washed with additional isopropyl alcohol.

[0560] Preparation 7 - Commercial PMMA (MX-180TA) (4 g) was sonicated with a solution of copper (II) 2-ethylhexanoate (0.21 g) in isopropyl alcohol and filtered washed with additional isopropyl alcohol.

[0561] Preparation 8 - Commercial PMMA (MX-180TA) (4 g) was sonicated with a solution of copper chloride (0.2 g) in isopropyl alcohol and vacuum filtered.

[0562] Example 4 - preparation of particle cores by emulsion polymerisation

[0563] The primary objective of the study was to prepare nano-microparticle cores by emulsion polymerization, specifically by emulsion polymerization of methacrylates. An exemplary reaction scheme is shown in Figure 18 Preparation was made using an oil-in-water emulsion of methacrylate in water in order to emulsion polymerize into nanoparticles.

[0564] Experiment 1 - Methyl methacrylate (3 mL) was added to deionized water (16 mL) to emulsify under inert gas at 70 °C. The polymerization reaction was catalyzed by ((2,2-azobis) 2-methyl- propionamidine) dihydrochloride (10 mg - 15 mg) and stirred for 30 minutes.

[0565] Experiment 2 - Methyl methacrylate (3 mL) was added to deionized water (16 mL) to emulsify under inert gas at 70 °C. The polymerization reaction was catalyzed by ((2,2-azobis) 2-methyl- propionamidine) dihydrochloride (10 mg - 15 mg) and stirred at 450 rpm for 40 minutes.

[0566] Experiment 3 - Methyl methacrylate (3 mL) was added dropwise to deionized water (16 mL) to emulsify under inert gas at 70 °C over 30 - 40 minutes. The polymerization reaction was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (10 mg - 15 mg) and stirred for 40 minutes.

[0567] Experiment 4 - Copper (II) 2-ethylhexanoate was dissolved in methyl methacrylate (3 mL) and injected into deionized water (16 mL) at 70 °C under inert gas. ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (10 mg - 15 mg) was added and stirred at 350 rpm for 40 minutes.

[0568] Example 5 - method for preparing hollow particle cores

[0569] This study demonstrates a method for preparing hollow particle-core structures. Representative SEM images of the hollow particles are shown in Figure 7 while representative SEM images of the hollow core particles combined with SPIONs and copper are shown in Figure 8 .

[0570] Experiment 1

[0571] A solution of 5% w / v - 6% w / v PMMA (120,000 g / mol) dissolved in dichloromethane (DCM) was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropyl alcohol and left to dry again.

[0572] Experiment 2

[0573] A solution of 5% w / v - 6% w / v PMMA (15,000 g / mol) dissolved in dichloromethane was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropyl alcohol and left to dry again.

[0574] Experiment 3

[0575] A first solution of copper (II) 2-ethylhexanoate (12.5 mg) dissolved in dichloromethane was prepared. A second solution of 5% w / v - 6% w / v PMMA (15,000 g / mol) dissolved in the first solution was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The final solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropyl alcohol and left to dry again.

[0576] Experiment 4

[0577] A dispersion of SPIONs (12.5 mg) in dichloromethane was prepared. 5% w / v - 6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropanol and again allowed to dry.

[0578] Experiment 5

[0579] A dispersion of SPIONs (12.5 mg) in dichloromethane was prepared. 5% w / v - 6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropanol and again allowed to dry.

[0580] Experiment 6

[0581] A dispersion of SPIONs (12.5 mg) in dichloromethane was prepared. 5% w / v - 6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5% w / v - 0.6% w / v) and stirred at 500 rpm - 550 rpm for 10 minutes - 15 minutes. The solution was left overnight or 12 hours - 18 hours until the DCM evaporated. The hollow particles were filtered washed three times with isopropanol and again allowed to dry.

[0582] Example 6 - method for preparing cores by combining susceptors and catalysts

[0583] The studies demonstrate the remote activation of microwave susceptors within matrix particles. The matrix used in these studies was prepared by combining the susceptors and other components of the matrix particle as a composite. The matrix particles were exposed to microwaves to release the activator to perform its function. For example, in some cases, the microwave heating of the susceptors, carbon nanostructures, releases a copper catalyst from the matrix particle to catalyze a polymerization reaction.

[0584] Experiment 1

[0585] Solution A was prepared by dissolving 5 g PMMA in xylene at 80 °C for 20-30 minutes. Solution B was prepared by melting 5 g of carnauba wax in xylene with a heat gun. A and B were combined very slowly while continuously heating. Copper (II) 2-ethylhexanoate (0.5%) was added to the solution of A and B. The solution was continuously stirred and heated to 110 °C until most of the xylene evaporated. Before all the xylene evaporated, 10% carbon nanostructures were added and mixed with high shear. Once enough xylene was evaporated to make the solution into a paste, the solution was poured abruptly into ethanol. The solid was broken up in a blender with water and dried overnight to obtain a powder. The powder was sieved through a micron screen to obtain core particles.

[0586] Experiment 2

[0587] A dispersion of 0.1 g carbon nanostructure pellets was prepared in 30 mL dichloromethane, then a solution of 3 g cetyltrimethylammonium bromide (CTAB) dissolved in 10 mL isopropyl alcohol and 20 mL dichloromethane was added while mixing at 700 rpm. Copper (II) 2-ethylhexanoate was added to the solution with 10 g of solid plasticizer (Benzoflex ™ 352) under continuous stirring. The sample was kept stirring until dry.

[0588] Experiment 3

[0589] A mixture of 0.1 g carbon nanotubes with 0.2 g CTAB in 30 mL dichloromethane was prepared and sonicated at 30% power for 15 minutes. Another 50 mL of dichloromethane was added and the sample was sonicated for another 15 minutes at 30%. 9.9 g Benzoflex ™ 352 (solid plasticizer) and 1 g copper (II) 2-ethylhexanoate were added and mixed by hand. A stir bar was added to the sample and stirred on a hot plate at 35 °C and 700 rpm to keep the particles suspended while the dichloromethane evaporated.

[0590] Experiment 4

[0591] A mixture of 0.11 g of Experiment 1 particles was dispersed in 10 mL of dimethyl malonate by sonication for 10 minutes. The particles were tested by placing one drop of the particles on a glass microscope slide and microwaving at 800 W / 4V for 60 seconds.

[0592] Example 7 - method for coating microparticles with susceptors

[0593] This study demonstrates a method for coating microparticles (e.g., commercial PMMA microparticles) with a susceptor such as carbon nanotubes (CNTs) or carbon nanostructures (CNSs).

[0594] Experiment 1

[0595] In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water. It was then sonicated for 30 minutes using a microprobe sonicator at 20% amplitude. In another flask, 300 mg of CNTs were added to 120 ml of water. It was sonicated for 15 minutes using a probe sonicator at 10% amplitude. The dispersion of PMMA and water was placed in a beaker and continuously stirred at room temperature to avoid settling of the PMMA particles. Next, 10 ml of the CNTs dispersed in water were placed in a syringe and added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0596] Experiment 2

[0597] In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water. It was then sonicated for 30 minutes using a microprobe sonicator at 20% amplitude. In another flask, 300 mg of CNTs were added to 120 ml of water. It was sonicated for 15 minutes using a probe sonicator at 10% amplitude. The dispersion of PMMA and water was placed in a beaker and continuously stirred at room temperature to avoid settling of the PMMA particles. Next, 10 ml of the CNTs dispersed in water were placed in a syringe and added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0598] Experiment 3

[0599] In this experiment, 1 ml of PMMA prepared using the emulsion polymerization method described previously was added to 9 ml of water. In another flask, 300 mg of CNTs were added to 120 ml of water. It was sonicated for 15 minutes using a microprobe sonicator at 10% amplitude. The dispersion of CNTs and water was placed in a beaker and continuously stirred at room temperature. Next, 10 ml of the PMMA dispersed in water was placed in a syringe and added dropwise to the CNT dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0600] Example 8 - method for preparing microparticles by emulsion copolymerisation

[0601] The present study provides a method of functionalizing PMMA by copolymerizing PMMA with various copolymers including poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) dimethacrylate (PEGDMA), stearyl methacrylate, and methacrylic acid.

[0602] Experiment 1

[0603] Methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 30-40 min. Additional 20 mg of AIBN was added with 1.2 mL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 min. PEGMA

[0604] Experiment 2

[0605] Methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 10 min. Additional 20 mg of AIBN was added with 1.2 mL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 min.

[0606] Experiment 3

[0607] Methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 10 min. Additional 20 mg of AIBN was added with 120 µL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 min.

[0608] Experiment 4

[0609] Methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 10 min. Additional 20 mg of AIBN was added with 120 µL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 min.

[0610] Dimethylacrylate (PEGDMA) and stir for 40 minutes. PEGDMA

[0611] Experiment 5

[0612] At 70 °C, methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 10 minutes. Additional 20 mg of AIBN was added with 1.2 mL of poly(ethylene glycol) dimethylacrylate (PEGDMA) and stirred for 40 minutes.

[0613] Experiment 6

[0614] A solution of sodium dodecyl sulfate (SDS) (0.5 g) dissolved in hydroxyethyl methacrylate (HEMA) (15 g) was prepared. This solution was transferred to a round bottom flask of deionized water (185 g) set in a hot bath at 70 °C and stirred at high speed. The heating was turned off while the solution was continuously stirred while AIBN (0.2 g) was added.

[0615] Experiment 7

[0616] A flask containing 64 mL of deionized water was degassed and heated to 70 °C while stirring its contents at 670 rpm for 20 minutes. Then, separately, 1 g of stearyl methacrylate was dissolved into 9 mL of methyl methacrylate. This solution was added dropwise into the water over 15 minutes in the presence of inert gas with continuous stirring. Once added, ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (40 mg) was added to the emulsion and the mixture / solution was stirred for an additional hour. Stearyl methacrylate

[0617] Experiment 8

[0618] A flask containing 64 mL of deionized water was degassed and heated to 70 °C while stirring its contents at 670 rpm for 20 minutes. Then, separately, 1 g of stearyl methacrylate was dissolved into 9 mL of methyl methacrylate. This solution was added dropwise into the water over 15 minutes in the presence of inert gas with continuous stirring. Once added, ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (40 mg) was added to the emulsion and the mixture / solution was stirred for an additional hour.

[0619] Experiment 9

[0620] A flask of 64 mL of deionized water was degassed and heated to 70 °C while stirring its contents at 670 rpm for 20 minutes. Next, 5 mL of methacrylic acid was dissolved into 5 mL of methyl methacrylate. This solution was added dropwise into the water over 15 minutes while continuing to stir under inert gas. Once added, ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (40 mg) was added to the emulsion and stirred for an additional hour. Methacrylic acid

[0621] Experiment 10

[0622] A flask of 64 mL of deionized water was degassed and heated to 70 °C while stirring its contents at 670 rpm for 20 minutes. Next, 5 mL of methacrylic acid was dissolved into 5 mL of methyl methacrylate. This solution was added dropwise into the water over 15 minutes while continuing to stir under inert gas. Once added, ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (40 mg) was added to the emulsion and stirred for an additional hour.

[0623] Experiment 11

[0624] Methyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 5 minutes. An additional 500 μL of glycidyl methacrylate (GMA) was added and stirred under inert gas for 40 minutes.

[0625] Experiment 12

[0626] Glycidyl methacrylate (12 mL) was added dropwise to deionized water (64 mL) at 70 °C to emulsify in the presence of inert gas. The polymerization was catalyzed by ((2,2-azobis) 2-methyl-propionamidine) dihydrochloride (AIBN) (20 mg) and stirred for 40 minutes.

[0627] Example 9 - method for coating commercially available microparticles with commercial emulsions

[0628] The purpose of this study was to coat commercial PMMA particles as the core with a shell containing sensitizer and / or activator by a simple coating process.

[0629] Experiment 1

[0630] In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. It was then sonicated in an ultrasonic apparatus for 30 minutes at 20% amplitude. At the same time, commercially manufactured SP-05032022-3: CNT dispersed in polyurethane was diluted 100 times and added to another beaker. The dispersion of PMMA and water was continuously stirred at room temperature to avoid PMMA particles settling. Then, 10 ml of CNT dispersed in polyurethane was added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. Then the particles were separated using a centrifuge.

[0631] Experiment 2

[0632] In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. It was then sonicated in an ultrasonic apparatus for 30 minutes at 20% amplitude. At the same time, commercially manufactured SP-05032022-3: CNT dispersed in polyurethane was diluted 100 times and added to another beaker. The dispersion of PMMA and water was continuously stirred at room temperature to avoid PMMA particles settling. Then, 10 ml of CNT dispersed in polyurethane was added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. Then the particles were separated using a centrifuge.

[0633] Experiment 3

[0634] In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. It was then sonicated in an ultrasonic apparatus for 30 minutes at 20% amplitude. At the same time, commercially manufactured SP-05032022-3: CNT dispersed in polyurethane was diluted 100 times and added to another beaker. The dispersion of PMMA and water was continuously stirred at room temperature to avoid PMMA particles settling. Then, 10 ml of CNT dispersed in polyurethane was added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. Then the particles were separated using a centrifuge.

[0635] Example 10 - method using carbon nanostructures as susceptors

[0636] This study demonstrated the use of commercial carbon nanostructures as radiofrequency (RF) radiation susceptors within the matrix particles to facilitate the release of catalysts to perform the function of catalyst-initiated polymerization reactions. For example, heating of the susceptors melts the matrix of the particles, which releases chemical ingredients such as copper salt catalysts to initiate polymerization. The purpose of this study was to use commercial PMMA particles as carriers of copper activators.

[0637] The particles generated in the experiments of this study were prepared by attaching the activators to the surface of the core of the matrix particles using commercial particles in the micrometer to nanometer scale as carriers of acrylic activators.

[0638] The microparticles from Example 6 above were used for the following heating time course measurements.

[0639] Experiment 1

[0640] The microparticles of Example 6 were taken and placed in an acrylic monomer formulation at 0.10 g / 3 g monomer, which consisted of 3 parts triacrylated monomer (OTA 480): 1 part multifunctional acrylic monomer (EBECRYL 898): 1 part polyurethane-acrylate (EBECRYL 8811) (all from Allnex Co) and 5000 ppm of 4-methoxyphenol (MEHQ), 2% cumene hydroperoxide (CHP) and 2% 4,N,N- trimethylaniline (DMPT). The data from the heating experiments are shown in Table 4 below. ® 896): 1 part polyurethane-acrylate (EBECRYL 8811) (all from Allnex Co) and 5000 ppm of 4-methoxyphenol (MEHQ), 2% cumene hydroperoxide (CHP) and 2% 4,N,N- trimethylaniline (DMPT). The data from the heating experiments are shown in Table 4 below. ® 896): 1 part polyurethane-acrylate (EBECRYL 8811) (all from Allnex Co) and 5000 ppm of 4-methoxyphenol (MEHQ), 2% cumene hydroperoxide (CHP) and 2% 4,N,N- trimethylaniline (DMPT). The data from the heating experiments are shown in Table 4 below.

[0641] Table 3: Heating time course data

[0642] Time (s) Temperature (°C) Temperature (°C) Temperature (°C) Average temperature (°C) 0 30 33 30 31 10 59 62 60 60 20 109 113 101 10 30 171 178 158 169

[0643] Example 11 - evaluation of the stability of particle cores prepared using CNS susceptors

[0644] Studies with foams

[0645] Foam cure tests were performed by cutting two pieces of foam into 4" x 4" cubes. The sample to be tested from Experiment 6 of Example 9 above was pipetted onto one piece of foam so that it uniformly covered one side of the cube, the layers being thick enough to stick to the pores of the foam. The second cube was placed on top of the first, completely covering the sample. The foam cubes were placed between two glass slides with spacers and held under even pressure by clamping the slides with rubber bands. The clamped sample was placed in the microwave chamber under the heat imager. To isolate the sample from direct heating, the sample was placed on an insulator in the microwave chamber. The sample was microwaved at 800W power for a preset amount of time. After the sample was removed from the microwave, the setup was carefully disassembled. To test whether the foams had bonded together, the corners of the foam were gently pulled apart.

[0646] Foam types tested :

[0647] ½ inch Airtex high density foam used to make camper mattresses, boat seats, chair cushions, garden benches, and small foam cushions.

[0648] 1 / 8 inch divinyl mat and ½ inch vinyl foam often used as structural core material for composite laminates, providing additional strength, stiffness, and thermal insulation without adding weight. Generally, the foam conforms easily to shape and can be bonded in layers to increase thickness.

[0649] Nomex honeycomb made from aramid fibers has excellent flammability.

[0650] Studies with composites

[0651] Bears shaped silicone molds were used to evaluate cure of bulk composites. The bear molds were filled one at a time with a 5cc volume and placed in the center of the microwave under the heat imager. Only one sample was placed at a time to ensure that the sample was in view of the heat imager. The bear molds were microwaved at 800W power for a preset amount of time and removed from the microwave to test for changes in viscosity or if cure had occurred.

[0652] Samples tested 1. Sample A: Acrylic adhesive formulation without activator (for formulation details, see Experiment 1 in Example 9 above) 2. Sample B: Acrylic adhesive formulation + copper activator 3. Sample C: Acrylic adhesive formulation + matrix particles (containing susceptor and copper activator)

[0653] Results of experiments with Airtex foam at room temperature: 1. Sample A: did not cure after one month; this sample contained no activator 2. Sample B: cured within 30 minutes 3. Sample C: cured within 30 seconds in the microwave, but at room temperature did not cure even after one month.

[0654] Results of experiments with divinyl felt, vinyl foam and honeycomb at room temperature: 1. Sample A: did not cure after one month; this sample contained no activator. 2. Sample B: cured within 30 minutes 3. Sample C: cured within 30 seconds in the microwave, but at room temperature did not cure even after one month.

[0655] Results of experiments with composites: 1. Sample A: did not cure after one month; this sample contained no activator. 2. Sample B: cured within 30 minutes. 3. Sample C: cured within 20 seconds in the microwave, but at room temperature did not cure even after one month.

[0656] This experimentally demonstrates the shelf life of the matrix particles of the present invention while still providing on-demand curing.

[0657] Example B1 : nanotube coated PMMA particles

[0658] According to U.S. Patent Application 18 / 055,302 to Malofsky et al., which is incorporated by reference as if fully set forth herein, the matrix particles are prepared with one or more types of nanotubes. Descriptions are also provided in the previous set of examples. For example, core PMMA particles of various sizes from 0.1 microns to 100 microns in diameter are prepared and coated with carbon nanotubes. These particles can or can not contain a catalyst, co-catalyst or promoter depending on the purpose for which the matrix particles are deployed.

[0659] The initial PMMA particles can be prepared by using emulsion polymerization, suspension polymerization, dispersion polymerization, seed swelling polymerization (see reference: European Polymer Journal 175 (2022) 111379 - Research progress of poly(methyl methacrylate) microspheres: Preparation, functionalization and application; Yafei Gao a, Jianmin Zhang, Jia Liang, Dongming Yuan, Weizhen Zhao).

[0660] For example, they can also be purchased from companies such as Sekisui or Soken in Japan. These particles can be prepared or obtained with various functional groups such as -OH, -NH, -COOH, epoxide, etc.

[0661] Nanotubes can be obtained from several manufacturers including cheap tubes.com, LG Chem (CNT division), and Tuball, Kumho petrochemicals.

[0662] Here we use the following PMMA particles :

[0663] PMMA product name Particle size MX-500ML 0.8 pm to 30 pm; average particle size: 5 pm MP-1441 0.15 pm to 0.4 pm; average particle size: 0.17 pm XX-6666Z Average particle size 4.7 pm MX-180TA 0.8 pm to 30 pm; average particle 1.8 pm 0.15 to 0.4 pm; average particle size: 0.17 pm MX-180TA 0.8 to 30 pm; average particle 1.8 pm XX-6666Z Average particle size 4.7 pm

[0664] **The MX-500ML, MP-1441, MX-180TA are derived from Soken in Japan and XX6666Z is derived from Sekisui kasei in Japan.

[0665] I. Method of making PMMA particles

[0666] Experiment B1.1 - At 70°C, methyl methacrylate (3 mL) was added to deionized water (16 mL) to emulsify under inert gas. The polymerization reaction was catalyzed by ((2,2-azobis) 2-methyl-propylamidine) dihydrochloride (10 mg - 15 mg) and stirred for 30 minutes.

[0667] Experiment B1.2: This study provides a method to functionalize PMMA by copolymerizing PMMA with various copolymers including poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) dimethacrylate (PEGDMA), stearyl methacrylate, and methacrylic acid.

[0668] II. Method of coating with nanotubes

[0669] This study demonstrates a method for coating microparticles (e.g., commercial PMMA microparticles) with sensitizer (such as carbon nanotubes (CNTs) or carbon nanostructures (CNSs)).

[0670] Experiment B1.3: In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water. It was then sonicated using a microprobe sonicator for 30 minutes at 20% amplitude. In another flask, 300 mg of CNTs were added to 120 ml of water. Using SDS surfactant, it was sonicated using a probe sonicator for 15 minutes at 10% amplitude. The PMMA and water dispersion was placed in a beaker and continuously stirred at room temperature to avoid PMMA particles from settling. In the next step, 10 ml of CNS dispersed in water was placed in a syringe and added dropwise to the PMMA dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0671] The particles containing 3.2 wt% of CNS prepared in experiment B1.3 were dispersed in an acrylic monomer formulation at concentrations of 25 wt% and 75 wt% of particles using a Flacktek speed mixer set at 2,000 RPM for 1 minute 30 seconds. The acrylic formulation comprised 3 parts of triacrylate monomer (OTA 480): 1 part of multifunctional acrylic monomer (EBECRYL 898): 1 part of polyurethane-acrylate (EBECRYL 8811) (all from Allnex Co) and 5000 ppm of 4-methoxyphenol (MEHQ), 2% of cumene hydroperoxide (CHP) and 2% of 4, N,N-dimethylaniline (DMPT). ® 896): 1 part of polyurethane-acrylate (EBECRYL ® 8811) (all from Allnex Co) and 5000 ppm of 4-methoxyphenol (MEHQ), 2% of cumene hydroperoxide (CHP) and 2% of 4, N,N-dimethylaniline (DMPT).

[0672] The acrylic formulation containing particles was degassed using a vacuum chamber for 30 minutes. Samples of 100% PMMA containing 3.2% CNS and acrylic formulations containing 0%, 25% and 75% particles were then applied at 4 mils onto 1 / 8 inch polycarbonate plates and pressed on a hot press set at 230 °F for 30 minutes. The resistivity of the cured films was measured using a surface resistivity meter and tabulated as shown in the table below:

[0673]

[0674] The relationship of resistivity to CNS loading shown in graph L2 indicates that the resistivity decreases from 1.0 x 10 13 to 6.0 x 10 3Ohms. This clearly demonstrates the effectiveness of the microparticles to deliver CNTs into the acrylic formulation.

[0675] Experiment B1.4: In this experiment, 1 ml of PMMA prepared using the emulsion polymerization method described previously was added to 9 ml of water. In another flask, 300 mg of CNTs were added to 120 ml of water. It was sonicated using a microprobe sonicator for 15 minutes at 10% amplitude. The dispersion of CNTs and water was placed in a beaker and continuously stirred at room temperature. Next, 10 ml of PMMA dispersed in water was placed in a syringe and added dropwise to the CNT dispersion using a syringe pump at 0.5 ml / min. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0676] Example B2: Making nanotube containing PMMA particles by incorporation

[0677] Experiment B2.1: Solution A was prepared by dissolving 5 g of PMMA in xylene at 80 °C for 20-30 minutes. Solution B was prepared by melting 5 g of Carnauba wax in xylene using a hot air gun. A and B were combined very slowly while continuously heating. Copper (II) 2-ethylhexanoate (0.5%) was added to the solution of A and B. The solution was continuously stirred and heated to 110 °C until most of the xylene evaporated. 10% carbon nanostructures were added and high shear mixed before all the xylene evaporated. Once enough xylene was evaporated to make the solution into a paste, the solution was poured abruptly into ethanol. The solid was broken up in a blender with water and dried overnight to obtain a powder. The powder was sieved through a micron screen to obtain core particles.

[0678] Example B3 Coating nanotube coated particles with functional nanoparticle emulsion

[0679] Particles from Example B1, once coated with nanotubes to the desired extent, are washed and dried or left in the solvent for subsequent coating reactions or processes with selected materials that interfere with van der Waals forces. (Applicant does not wish to be bound by any theory discussed in this disclosure.) In this nanowax, epoxide and PUD (polyurethane dispersion) are nano-particle emulsions and dispersions, respectively. PUD was purchased from Covestro and epoxide emulsion was purchased from Westlake.

[0680] Functional nano-particle emulsions and dispersions are available from manufacturers including Michelman, Covestro, BYK, and Westlake.

[0681] Here we use the following functional nano-particle emulsions and or dispersions: A. ME98040M1 (Michelaman) B. EPI-REZ 3514-W-56 (Westlake) C. Baybond PU 405 (Covestro) D. Aqacer 581, 532, 1061 (BYK)

[0682] Experiment B3.1: Water solutions of functional nanoparticle emulsions and dispersions were added dropwise to 250 mg of particles from Example B1 using a syringe pump. The samples were left overnight to allow the coated particles to settle. The particles were then separated using a centrifuge.

[0683] Example B4: Coating nanotube coated particles with monofunctional reactive material

[0684] Particles from Example 1, once coated to the desired extent with nanotubes, were washed and dried or left in the solvent for subsequent coating reactions or processes with selected materials that interfere with van der Waals forces, in this case using a monofunctional reactive material. These studies can be done by varying the length of the aliphatic chain.

[0685] These are common materials readily available from manufacturers such as BASF and Evonik, as well as common materials for laboratory experiments from Sigma Aldrich.

[0686] Exemplary materials include: A. Stearic acid B. Octanoic acid C. Oleic acid D. Stearyl alcohol E. Aliphatic amines F. Chitosan G. Dioctylamine, Hexadecylamine

[0687] Experiment B4.1: Particles from Experiment B1.3 containing alcohol functional groups were suspended in anhydrous MEK (methyl ethyl ketone) or isopropyl acetate, dimethyl carbonate, cyclohexanone, 2-methyltetrahydrofuran. Solvents were chosen in which the particles were insoluble. They were reacted with oleic acid, stearic acid, and octanoic acid or other branched or straight chain fatty acids under standard Steglich-type esterification conditions.

[0688] Experiment B4.2: Particles from Experiment B1.3 containing acid functional groups were suspended in the anhydrous solvents described in Experiment 4.1 and reacted with fatty alcohols not limited to stearyl alcohol under standard Steglich-type esterification conditions.

[0689] Experiment B4.3: Particles from Experiment B1.3 containing epoxy functional groups were suspended in the anhydrous solvents described in Experiment B4.1 and reacted with aliphatic primary and secondary amines not limited to dioctylamine and hexadecylamine.

[0690] Example B5: Coating nanotube coated particles with difunctional material

[0691] Particles from Example B1, once coated with nanotubes to the desired extent, are washed and dried or left in solvent for subsequent coating reactions or processes with selected materials that interfere with van der Waals forces, in this case using a monofunctional reactive material. These studies can be carried out by varying the length of the intermittent aliphatic chain containing the difunctional material. One is a reactive functional group and the other is a protective (non-interfering) functional group. The reactive functional group is designed to react with the particles from Example B1 and the protected functional group is left outside for further crosslinking operations.

[0692] These are common materials readily available from manufacturers such as BASF and Evonik, as well as common materials for laboratory experiments Sigma Aldrich.

[0693] Exemplary materials include: A. Adipic acid B. Adipic acid half ester C. Propylene diamine D. Ethylene diamine E. BOC mono-protected propylene diamine

[0694] Experiment B5.1: Particles containing alcohol functional groups from Experiment B1.3 are suspended in anhydrous MEK (methyl ethyl ketone) or isopropyl acetate, dimethyl carbonate, cyclohexanone, 2-methyltetrahydrofuran. Solvents are chosen in which the particles are not soluble. They are reacted with difunctional carboxylic acids such as adipic acid or adipic acid half ester.

[0695] Experiment 5.2: Particles containing acid functional groups from Experiment B1.3 are suspended in anhydrous solvents described in Experiment B4.1 and reacted with propylene diamine using carbodiimide / HOBt coupling.

[0696] Example B6: Viscosity effect - blending materials with carbon nanotubes, carbon nanotube coated or containing particles and coated carbon nanotube coated or containing particles

[0697] Here we demonstrate that carbon nanotubes and / or carbon nanotube coated particles have very high viscosity due to the associative van der Waals effect, while coated particles do not, especially those with a repulsive coating.

[0698] Procedure: Particles from Examples B1, B2, B3, B4 and B5 are mixed into polymerizable compositions for coatings and adhesives using higher shear, ultrasonic treatment and rapid mixing processes. The viscosity of the resulting materials is measured using a Ford cup or Brookfield viscometer.

[0699] Example B7 Performance effect - I

[0700] In one embodiment, the present invention is directed to blending a polymerizable composition with carbon nanotube coated and / or containing particles, polymerizing the matrix, and evaluating the physical impact on strength, impact resistance, modulus, toughness, etc.

[0701] Here, we demonstrate that for lower cost, simpler, easier processing and loading, carbon nanotube coated and / or containing particles now having lower viscosity thus also provide slightly lower, the same or improved physical properties in the final polymerized composition.

[0702] Procedure: Cure the polymerizable composition described in Example B6 under standard conditions. Test the resulting coating for hardness properties, for example, by indentation and tabber abrasion testing. Cross hatch adhesion testing and visual comparison to standard.

[0703] Cast and cure the polymerizable composition containing particles into a thin film and test for tensile, flexural strength and modulus. Dynamic mechanical analysis (DMA) is used to measure the viscoelastic response of a sample under oscillating loads, monitored as a function of temperature, time or frequency.

[0704] Example B8 Performance effect - II

[0705] In one embodiment, the present invention is directed to blending a polymerizable composition comprising: (i) carbon nanotube coated particles; (ii) chemically functionalized carbon nanotube coated particles; (iii) particles comprising carbon nanotubes and / or (iv) chemically functionalized particles comprising carbon nanotubes. In the next step, this polymerizable composition is polymerized and its physical impact on strength, impact resistance, modulus, toughness, etc. is measured.

[0706] Here, we demonstrate that for lower cost, simpler, easier processing and loading, the above particles provide a material having lower viscosity and then also provide slightly lower, the same or improved physical properties in a polymerizable or partially reactive polymer composition where the particles are now at least partially chemically bound to the above polymer matrix.

[0707] Test the polymerized matrix by DMA according to ASTM D4065, D4440, D5279. Measure the elastic modulus (or storage modulus, G'), viscous modulus (or loss modulus, G'') and damping factor (Tan D) as a function of temperature, frequency or time.

[0708] Test the polymerized matrix according to:

[0709] ASTM D638 / D-882 - Tensile Properties

[0710] ASTM D790 - Flexural Properties of Plastics

[0711] ASTM D256 - Izod Impact Resistance of Plastics

[0712] ASTM D4812 - Impact Resistance of Unnotched Cantilever Beams in Plastics

[0713] Example Group C

[0714] C1. Synthesis of CNT modified PMMA brush microparticles by bottom up approach

[0715] This study demonstrates a method for preparing CNT-modified "brush-like" microparticles starting from MMA monomers and constructing micron-scale cores from monomers using a bottom-up approach. The CNTs on the surface provide a convenient method for delivering CNTs into polymer resin matrices for reinforcement.

[0716] Prepare a 60 mL SDS solution (0.1 mg / mL) in deionized (DI) water, followed by the addition of methanol (30 mL). Add polyvinylpyrrolidone (PVP) (2.5 g) to the mixture and stir until dissolved. Then introduce azobisisobutyronitrile (AIBN) (0.2 g) into the solution and dissolve. In a separate container, sonicate a dispersion of CNT (4 mL) and surfactant (D-1038) (4 drops) in methanol (5 mL) for 10 minutes to homogenize.

[0717] The ultrasonically treated CNT solution was slowly added to the reaction mixture containing PVP, methanol, and AIBN while continuously stirring. After stirring for 10 minutes, methyl methacrylate (MMA) (20 g) was slowly added to the reaction batch while maintaining a constant temperature of 70°C. The reaction was allowed to proceed at 70°C for 3 hours to ensure complete polymerization and particle formation within the CNT dispersion. Upon completion of the reaction, the formed micron-sized particles were filtered from the reaction mixture.

[0718] C2. Modification of commercial microparticles for making brush particles with a shell

[0719] This study demonstrates a method for preparing CNT-modified "brush-like" microparticles from commercially available PMMA particles. The CNTs on the surface of the microparticles provide a convenient method for delivering CNTs into a polymer resin matrix for reinforcement.

[0720] Commercial PMMA particles (50g-60g) with a diameter ranging from 1 micron to 5 microns were dispersed in a solution of Epoxy 1007F resin in 60 mL of tetrahydrofuran (THF) (10% concentration). The PMMA particles were stirred until a uniform dispersion was obtained. An ethanol solution of CNT dispersion was added and stirring was continued for an additional hour at 50 °C. The procedure was continued by slowly injecting the dispersion of PMMA particles in epoxy resin into a solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP) at a concentration of 1%.

[0721] C3. Modification of commercial microparticles for making brush particles with a low melting point

[0722] Commercial PMMA particles with a diameter ranging from 1 micron to 5 microns were dispersed in a solution of Epoxy 1004F resin and THF (10% concentration). The PMMA particles were dispersed in the resin solution and stirred until uniform. An ethanol solution of CNT dispersion was added and stirring was continued for an additional hour at 50 °C. The procedure was continued by slowly injecting the dispersion of PMMA particles in epoxy resin into a solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP) at a concentration of 1%.

[0723] C4. Modification of commercial microparticles for making brush particles with a low melting point

[0724] Commercial PMMA particles with a diameter ranging from 1 micron to 5 microns were dispersed in a solution of Epoxy 1004F resin and THF (10% concentration). The PMMA particles were dispersed in the resin solution and stirred until uniform. An ethanol solution of CNT dispersion was added and stirring was continued for an additional hour at 50 °C. The procedure was continued by slowly injecting the dispersion of PMMA particles in epoxy resin into a solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP) at a concentration of 1%.

[0725] C5. Burrowed microparticles

[0726] This study demonstrates a method for preparing an embedded particle-core structure starting from commercial micron particles. The embedded particles are used as the core of the matrix particles. The embedding process involves treating the micron particles with a solvent such as IPA (isopropyl alcohol). The osmotic pressure at the surface of the micron particles and the evaporation of the solvent embeds pores in the micron particles. Hydrophobic interactions cause the catalyst and / or CNT / CNS to migrate into the embedded burrows. The embedded micron particles are converted into core-shell micron particles. The resulting core-shell micron particles provide the advantage of delivering CNTs into the polymer resin.

[0727] C6. Burrowed core-shell microparticles with a PMMA shell

[0728] A solution of polyvinyl alcohol (PVOH) (2 g) in deionized water (400 g) was prepared. Separately, a dispersion of CNT (0.8 g) in isopropyl alcohol (100 g) was prepared. Ten (10) g of commercial micron particles (1 micron - 10 microns) were added and dispersed into the PVOH solution. The CNT dispersion was added to the PVOH solution. The dispersion was stirred for 12-18 hours until the IPA (isopropyl alcohol) evaporated. The osmotic pressure of the IPA during the 12-18 hours created embedding pores on the surface of the micron particles. As the solvent evaporated, the CNT migrated into the embedding pores due to hydrophobic interactions. The dried embedding micron particles containing CNT were added to clean water. Stearyl methacrylate (5 g) was added dropwise and emulsion polymerization was carried out in the presence of inert gas. The emulsion polymerization reaction was catalyzed by azobisisobutyronitrile (AIBN) (20 mg) and stirred for 40 minutes to form a PMMA shell.

[0729] C7. Burrowed core-shell microparticles with a PGMA shell

[0730] A solution of polyvinyl alcohol (PVOH) (2 g) in deionized water (400 g) was prepared. Separately, a dispersion of CNT (0.8 g) in isopropyl alcohol (100 g) was prepared. Ten (10) g of commercial micron particles (1 micron - 10 microns) were added and dispersed into the PVOH solution. The CNT dispersion was added to the PVOH solution. The dispersion was stirred for 12-18 hours until the IPA (isopropyl alcohol) evaporated. The osmotic pressure of the IPA during the 12-18 hours created embedding pores on the surface of the micron particles. As the solvent evaporated, the CNT migrated into the embedding pores due to hydrophobic interactions. The dried embedding micron particles containing CNT were added to clean water. Glycidyl methacrylate (GMA) (5 g) was added dropwise and emulsion polymerization was carried out in the presence of inert gas. The emulsion polymerization reaction was catalyzed by azobisisobutyronitrile (AIBN) (20 mg) and stirred for 40 minutes to form a PGMA shell.

[0731] C8. Burrowed microparticles with a PSMA shell produced by emulsion polymerization .

[0732] A solution of polyvinyl alcohol (PVOH) (2 g) in deionized water (400 g) was prepared. Separately, a dispersion of CNT (0.8 g) in isopropyl alcohol (100 g) was prepared. Ten (10) g of commercial micron particles (1 micron - 10 microns) were added and dispersed into the PVOH solution. The CNT dispersion was added to the PVOH solution. The dispersion was stirred for 12-18 hours until the IPA evaporated. The osmotic pressure of the IPA created an embedded pore on the surface of the micron particles during the 12-18 hours. As the solvent evaporated, the CNT migrated into the embedded pore due to hydrophobic interactions. The dried embedded micron particles containing CNT were added to clean water. Stearyl methacrylate (SMA) (5 g) was added dropwise and emulsion polymerization was carried out in the presence of inert gas. The emulsion polymerization reaction was catalyzed by azobisisobutyronitrile (AIBN) (20 mg) and stirred for 40 minutes to form a PSMA shell.

[0733] C9. Burrowed core-shell microparticles with a PU shell

[0734] A solution of polyvinyl alcohol (PVOH) (2 g) in deionized water (400 g) was prepared. Separately, a solution of copper 2-ethylhexanoate (0.8 g) in isopropyl alcohol (100 g) was prepared. Ten (10) g of commercial micron particles were added and dispersed into the PVOH solution. The copper solution was added to the PVOH solution. The dispersion was stirred for 12-18 hours until the IPA evaporated. The osmotic pressure of the IPA created an embedded pore on the surface of the micron particles during the 12-18 hours. As the solvent evaporated, the copper 2-ethylhexanoate migrated into the embedded pore due to hydrophobic interactions. A solution of commercial polyurethane-CNT (10 mL) in acetone was mixed into the dispersion as a coating for the embedded particles.

Claims

1. A plurality of matrix particles, said matrix particles including matrix particle A and / or matrix particle B: in, The matrix particle A includes a core and optionally at least one shell. The core comprises: (i) a matrix material, wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties; (ii) at least one receptor component, wherein the at least one receptor component is embedded in the matrix material; as well as (iii) at least one releasable component, wherein the at least one releasable component is embedded in the matrix material, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles, and The at least one shell comprises: (iv) Optionally, the at least one receptor component, wherein the at least one receptor component is embedded in the at least one shell; and (v) at least one releasable component, wherein the at least one releasable component is embedded in the at least one shell, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles; and The matrix particle B comprises a core and optionally at least one shell, wherein the core comprises: (vi) a matrix material, wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties; and (vii) At least one releasable component, wherein the at least one releasable component is embedded in the matrix material, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles; and The at least one shell comprises: (viii) Optionally, the at least one receptor component, wherein the at least one receptor component is embedded in the at least one shell; and (ix) the at least one releasable component, wherein the at least one releasable component is embedded in the at least one shell, wherein the at least one releasable component is capable of physically or chemically influencing the bulk physical or chemically variable composition in contact with the plurality of matrix particles; and The at least one sensor component and / or the releasable component can be activated by radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical wear, or a combination thereof.

2. The various matrix particles according to claim 1, wherein the matrix material is derived from and / or comprises organic, monomeric, oligomeric, polymeric materials or combinations thereof.

3. The various matrix particles according to any one of the preceding claims, wherein the at least one receptor and / or the at least one releasable component is selected from the group consisting of: fullerene compounds, graphene, graphene oxide, nanocrystalline cellulose, single-walled carbon nanotubes, multi-walled 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 materials, boron nitride, and one or more combinations thereof.

4. A plurality of matrix particles according to any one of the preceding claims, wherein the size of the at least one receptor and / or the at least one releasable component is in the range of about 0.1 nm to about 1000 µm, and optionally, the at least one receptor and / or the at least one releasable component is functionalized and / or unfunctionalized.

5. A plurality of matrix particles according to any one of the preceding claims, wherein the at least one receptor and / or the at least one releasable component is contained in the at least one shell, and wherein the at least one receptor and the at least one releasable component are in direct or indirect contact.

6. A plurality of matrix particles according to any one of the preceding claims, wherein the matrix particles are partially or wholly coated in one or more layers of deformable material, wherein, Optionally, one or more of the layers contain the at least one receptor and / or the at least one releasable component.

7. The matrix particles according to any one of the preceding claims, wherein the at least one releasable component is a single chemical, a combination of chemicals, an organic chemical and / or an inorganic chemical, and wherein the at least one releasable component includes one or more catalysts, co-catalysts, co-reactants, oxidants, reaction inhibitors, promoters, co-promoters, fuels, explosives or one or more combinations thereof.

8. The plurality of matrix particles according to any one of the preceding claims, wherein the at least one releasable component is released when the matrix material or the shell is deformed, dissolved, melted, expanded, contracted, ruptured, plasticized, solvated, affected by light, or one or more combinations thereof.

9. A plurality of matrix particles according to any one of the preceding claims, wherein the particles are further chemically surface modified via one or more chemical reactions, optionally containing the at least one releasable component, and then optionally forming a partial or complete coating.

10. A plurality of matrix particles according to any one of the preceding claims, the plurality of matrix particles having chemical functional groups, wherein the at least one releasable component comprises a chemical functional monomer, wherein the matrix material comprises a polymeric material, and optionally, the matrix particles are coated with a polymeric coating.

11. A plurality of matrix particles according to any one of the preceding claims, wherein one or more variable matrix materials include wax, one or more of the following: polymethyl methacrylate (PMMA), other substituted acrylates, styrene, or one or more polymers or copolymers thereof.

12. A method for preparing a plurality of matrix particles according to any one of the preceding claims using methods A, B, C, D, or combinations thereof, wherein: (A) includes emulsion polymerization, dispersion polymerization, and / or suspension polymerization; or (B) includes core-shell polymerization; or (C) includes copolymerization, wherein the copolymerization step includes emulsion polymerization, dispersion polymerization, suspension polymerization, or a combination thereof; (D) includes the following steps: (i) Coating polymer microparticles with a material containing receptors and releasable components. (ii) Encapsulating micron-sized particles containing sensors and releasable components within monomeric, oligomeric, or polymeric materials, and / or (iii) Combining the receptor and the releasable component, and (iv) The receptor and the releasable component are embedded in the external pores on the surface of the porous microsphere or in the internal pores in the core of the porous microsphere.

13. A method for influencing a chemical reaction or a method for releasing at least one releasable component from a plurality of matrix particles, said method comprising: (i) Provide the bulk reaction mixture; (ii) Providing matrix particles according to claims 1 to 11; (iii) Incorporating the various matrix particles into the bulk reaction mixture; as well as (iv) Optionally incorporate the plurality of matrix particles into the bulk reaction mixture and bombard the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the receptor components embedded in the matrix particles; Heating the bulk reaction mixture containing the various matrix particles; Mechanical milling of the bulk reaction mixture comprising the plurality of matrix particles; or Their combination.

14. The matrix particles according to any one of claims 1 to 11, wherein CNTs are incorporated into the matrix particles by the method according to claim 12.

15. An article comprising a plurality of matrix particles according to any one of claims 1 to 11 and 14.

16. The article prepared according to claim 12, wherein all or part of the article comprises: (i) a polymerizable composition of at least one chemical substance or several polymerizable compositions; (ii) Reinforced composite material products; (iii) Laminated products; (iv) Rigid laminates; (v) Flexible laminated products; (vi) foam; or (vii) Their combination.

17. A composition comprising a plurality of matrix particles according to any one of claims 1 to 11 and 14, wherein the composition is wholly or partially an adhesive, sealant, coating, paint, ink, plastic, molding plastic, thermosetting plastic, molding thermosetting plastic or other polymer-formed composition.

18. The matrix particles according to any one of claims 1 to 11 and 14, wherein the releasable component is a catalyst selected from the group consisting of: transition metal complexes; transition metal alkoxides; bis(2-ethylhexanoate) stannous(II); carboxylates, alkoxides and complexes of stannous, bismuth, zinc, and titanium; blocked superacids; dodecylbenzenesulfonic acid; dinonylnaphthalenesulfonic acid; N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine; organic bases; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,5-diazabicyclo[4.3.0]nonene-5); (1,4-diazabicyclo2.2.2octane); and combinations thereof.

19. A multilayer polymer composition comprising a first plurality of matrix particles according to any one of claims 1 to 11, 14 and 18, and one or more additional plurality of matrix particles according to any one of claims 1 to 11 and 14 disposed on the first matrix particles, thereby forming one or more matrix particle layers.

20. A precursor, intermediate, or final monomer, oligomer, or polymer composition comprising a plurality of matrix particles according to any one of claims 1 to 11 and 14, wherein the composition is solid-state polymerized or prepared from a reactive hot-melt formulation.

21. The plurality of matrix particles according to any one of claims 1 to 11, 14 and 18, wherein the plurality of matrix particles comprise carbon nanotubes, wherein the carbon nanotubes are coated on the matrix particles and / or contained in the matrix particles.

22. The plurality of matrix particles according to any one of claims 1 to 11, 14 and 18, wherein the CNTs are incorporated into the plurality of matrix particles through the merging process.

23. The matrix particles according to any one of claims 1 to 11, 14 and 18, wherein the matrix particles are further coated with a functional nanoparticle emulsion or dispersion.

24. The matrix particles according to any one of claims 1 to 11, 14 and 18, wherein the matrix particles are further coated with a monofunctional reactive material or a bifunctional reactive material.

25. A precursor, intermediate, or final monomer, oligomer, or polymer composition comprising a plurality of matrix particles according to any one of claims 1 to 11, 14, and 18; optionally, wherein the composition is prepared from a functionalized polymer formulation, and optionally, wherein the composition is prepared as a reactive blend with a non-reactive polymer or oligomer.

26. A method for influencing a chemical reaction, the method comprising: (i) Provide the bulk reaction mixture; (ii) Providing a variety of matrix particles according to any one of claims 1 to 11, 14 and 18; (ii) Incorporating the plurality of matrix particles into the bulk reaction mixture and bombarding the bulk reaction mixture at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the receptor components embedded in the matrix particles; Heating the bulk reaction mixture containing the various matrix particles; Mechanical milling of the bulk reaction mixture comprising the plurality of matrix particles; or Their combination; The bulk reaction mixture is a precursor or intermediate monomer, oligomer, or polymer composition for solid-state polymerization; The bulk reaction mixture is a precursor or intermediate monomer, oligomer, or polymer composition for reactive hot melt formulations; The bulk reaction mixture is a precursor or intermediate monomer, oligomeric or polymeric composition for use in reactive blends with non-reactive polymers or oligomers; or The bulk reaction mixture is a precursor or intermediate monomer, oligomer, or polymer composition for use in functionalized polymer formulations.

27. A method for increasing the total loading of CNTs in a bulk physically or chemically variable composition, said method being carried out by the method according to any one of the preceding claims 29.

28. A method for maintaining a low viscosity when adding at least one additive to a bulk physically or chemically variable composition, the method comprising incorporating the at least one additive as at least one releasable component into a plurality of matrix particles according to claims 1 to 11, 14 and 18, and incorporating the plurality of matrix particles into the bulk physically or chemically variable composition.

29. A method for increasing the total loading of an additive in a bulk physically or chemically variable composition, the method comprising: (i) Provide the bulk physical or chemically variable composition; (ii) incorporating the at least one additive as a releasable component into the various matrix particles according to claims 1 to 11, 14 and 18; (ii) Incorporating the plurality of matrix particles into the bulk physical or chemically variable composition, and bombarding the bulk physical or chemically variable composition at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the sensor components embedded in the matrix particles; Heating the bulk physical or chemically variable composition comprising the various matrix particles; Mechanical grinding of the bulk physical or chemically variable composition comprising the aforementioned matrix particles; or Their combination; Optionally, the bulk physical or chemically variable composition is a precursor or intermediate monomer, oligomer, or polymer composition for reactive hot melt formulations, adhesives, coatings, or composites, or a combination thereof.

30. A method for maintaining a low viscosity when adding at least one additive to a bulk physically or chemically variable composition, the method comprising the steps of: (i) Provide the bulk physical or chemically variable composition; (ii) incorporating the at least one additive as a releasable component into the various matrix particles according to claims 1 to 11, 14 and 18; (ii) Incorporating the plurality of matrix particles into the bulk physical or chemically variable composition, and bombarding the bulk physical or chemically variable composition at least once with RF radiation of at least one frequency and / or MW radiation of at least one frequency to thermally activate the sensor components embedded in the matrix particles; Heating the bulk physical or chemically variable composition comprising the various matrix particles; Mechanical grinding of the bulk physical or chemically variable composition comprising the aforementioned matrix particles; or Their combination; Optionally, the bulk physical or chemically variable composition is a precursor or intermediate monomer, oligomer, or polymer composition for reactive hot melt formulations, adhesives, coatings, or composites, or a combination thereof.

31. The matrix particles according to any one of claims 1 to 11 and 14, wherein the releasable component is a catalyst for curing, polymerization, acrylate reaction, silane-terminated polymer, hydrolysis, condensation catalyst, isocyanate trimerization, 1K moisture-cured isocyanate, melamine crosslinking system, 2K polyurethane, 1K-terminated isocyanate-based polyurethane, epoxide, esterification and transesterification.

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